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81.
The kinetics of substitution reactions of [η-CpFe(CO)3]PF6 with PPh3 in the presence of R-PyOs have been studied. For all the R-PyOs (R = 4-OMe, 4-Me, 3,4-(CH)4, 4-Ph, 3-Me, 2,3-(CH)4, 2,6-Me2, 2-Me), the reactions yeild the same product [η5-CpFe(CO)2PPh3]PF6, according to a second-order rate law that is first order in concentrations of [η5-CpFe(CO)3]PF6 and of R-PyO but zero order in PPh3 concentration. These results, along with the dependence of the reaction rate on the nature of R-PyO, are consistent with an associative mechanism. Activation parameters further support the bimmolecular nature of the reactions: ΔH≠ = 13.4 ± 0.4 kcal mol−1, ΔS≠ = −19.1 ± 1.3 cal k−1 mol−1 for 4-PhPyO; ΔH≠ = 12.3 ± 0.3 kcal mol−1, ΔS≠ = 24.7 ±1.0 cal K−1 mol−1 for 2-MePyO. For the various substituted pyridine N-oxides studied in this paper, the rates of reaction increase with the increasing electron-donating abilities of the substituents on the pyridine ring or N-oxide basicities, but decrease with increasing 17O chemical shifts of the N-oxides. Electronic and steric factors contributing to the reactivity of pyridine N-oxides have been quantitatively assessed. 相似文献
82.
The photosynthetic performance of a helical tubular photobioreactor ("Biocoil"), incorporating the filamentous cyanobacterium Spirulina platensis, was investigated. The photobioreactor was constructed in a cylindrical shape (0.9 m high) with a 0.25-m(2)basal area and a photostage comprising 60 m of transparent PVC tubing of 1.6-cm inner diameter (volume = 12.1 L). The inner surface of the cylinder (area = 1.32 m(2)) was illuminated with cool white fluorescent lamps; the energy input of photosynthetically active radiation(PAR, 400 to 700 nm) into the photobioreactor was 2920 kJ per day. An air-lift system ncorporating 4%CO(2) was used to circulate the growth medium in the tubing. The maximum productivity achieved in batch culture was 7.18 g dry biomass per day [0.51 g . d biomass/L . day, or 5.44 g . d biomass/m(2)(inner surface of cylindrical shape)/day] which corresponded to a photosynthetic (PAR) efficiency of 5.45%. The CO(2) was efficiently removed from the gaseous stream; monitoring the CO(2) the outlet and inlet gas streams showed a 70% removal of CO(2) from the inlet gas over an 8-h period with almost maximum growth rate. (c) 1995 John Wiley & Sons, Inc. 相似文献
83.
Most biological substrates have distinctive sizes, shapes, and charge distributions which can be recognized specifically
by proteins. In contrast, myoglobin must discriminate between the diatomic gases O2, CO, and NO which are apolar and virtually the same size. Selectivity occurs at the level of the covalent Fe-ligand complexes,
which exhibit markedly different bond strengths and electrostatic properties. By pulling a water molecule into the distal
pocket, His64(E7)1 inhibits the binding of all three ligands by a factor of ∼10 compared to that observed for protoheme-imidazole complexes
in organic solvents. In the case of O2 binding, this unfavorable effect is overcome by the formation of a strong hydrogen bond between His64(E7) and the highly
polar FeO2 complex. This favorable electrostatic interaction stabilizes the bound O2 by a factor of ∼1000, and the net result is a 100-fold increase in overall affinity compared to model hemes or mutants with
an apolar residue at position 64. Electrostatic interaction between FeCO and His64 is very weak, resulting in only a two-
to three-fold stabilization of the bound state. In this case, the inhibitory effect of distal pocket water dominates, and
a net fivefold reduction in K
CO is observed for the wild-type protein compared to mutants with an apolar residue at position 64. Bound NO is stabilized ∼tenfold
by hydrogen bonding to His64. This favorable interaction with FeNO exactly compensates for the tenfold inhibition due to the
presence of distal pocket water, and the net result is little change in K
NO when the distal histidine is replaced with apolar residues. Thus, it is the polarity of His64 which allows discrimination
between the diatomic gases. Direct steric hindrance by this residue plays a minor role as judged by: (1) the independence
of K
O2, K
CO, and K
NO on the size of apolar residues inserted at position 64, and (2) the observation of small decreases, not increases, in CO
affinity when the mobility of the His64 side chain is increased. Val68(E11) does appear to hinder selectively the binding
of CO. However, the extent is no more than a factor of 2–5, and much smaller than electrostatic stabilization of bound O2 by the distal histidine.
Received, accepted: 23 May 1997 相似文献
84.
L J Young O Einarsdóttir C R Vossbrink W S Caughey 《Biochemical and biophysical research communications》1984,123(1):247-253
Infrared bands for CO bound to mitochondria from bovine and porcine hearts, bovine brain, rat kidney, and blowfly flight muscle and to intact blowfly flight muscle have been measured in the carbon-oxygen stretch region. Each spectrum contains a narrow band near 1963 cm-1 similar to the major band found earlier for the carbonyl cytochrome c oxidase purified from bovine heart. A second band near 1959 cm-1 ascribed to a less stable conformer of the purified oxidase carbonyl is also detected in mitochondria. These spectra support very similar CO (and O2) binding sites among all the oxidases examined whether the enzyme is purified or is still within mitochondria or intact tissue and therefore suggest that the reduced heme A ligand binding site has been highly conserved during evolution. 相似文献
85.
Davey K. G., Sommerville R. I. and Rogers W. P. 1982. The effect of ethoxyzolamide, an analogue of insect juvenile hormone, nor-adrenaline and iodine on changes in the optical path difference in the excretory cells and oesophagus during exsheathment in Haemonchus contortus. International Journal for Parasitology12: 509–513. Ethoxyzolamide, an inhibitor of carbonic anhydrase, markedly inhibits exsheathment of Haemonchus when the larvae are subsequently exposed to an exsheathing stimulus of CO2 at 38.5°C. Ethoxyzolamide at 2 × 10?5M does not prevent the increase in optical path difference in the oesophageal region which normally accompanies exsheathment, but markedly inhibits the increase in optical path difference in the excretory cells. An analogue of juvenile hormone (JHA; the methyl ester of 3,7,11 trimethyl-7,11-dichloro-2-dodecenic acid) does not affect the optical path difference in either the oesophagus or the excretory cells of ensheathed worms. When worms are artificially desheathed by exposure to NaOCl, a procedure which mimics the effect of CO2 upon the oesophagus, but which does not affect the excretory cells, subsequent exposure to JHA at room temperature increases the optical path difference in the excretory cells. This increase is enhanced by subsequent incubation of the worms at 38.5°C at 30–60 min and further enhanced when CO2 is present during the incubation at 38.5°C. The stimulation of the excretory cells by JHA is inhibited by ethoxyzolamide at 2 × 10?5M. Noradrenaline at 10?3M has no effect on ensheathed larvae, but causes an increase in optical path difference in the excretory cells of larvae desheathed with NaOCl. This increase is inhibited by ethoxyzolamide. A brief exposure to I2 blocks the response of the excretory cells of both CO2 and JHA, but does not significantly reduce the effect of nor-adrenaline. On the basis of these and previous results, it is proposed that both CO2 and JHA stimulate a hypothetical CO2 receptor which leads to the release of nor-adrenaline. The noradrenaline in turn stimulates, either directly or indirectly, the excretory cells. 相似文献
86.
Photosynthetic induction in wheat protoplasts and chloroplasts. Autocatalysis and light activation of enzymes 总被引:1,自引:0,他引:1
Abstract Unlike wheat chloroplasts, wheat protoplasts showed a pronounced restoration of the induction phase after a short period of darkness. This difference was used to investigate the relative roles of light-induced reductive activation of enzymes and the auto-catalytic increase in the level of substrates in the control of the rate of photosynthesis during induction. Light activation and dark inactivation of ribulose 5-phosphate kinase, fructose 1,6-biphosphatase and NADP+-specific glyceraldehydephosphate dehydrogenase were measured. In this respect there was no appreciable difference between protoplasts and chloroplasts. In contrast, the level of photosynthetic intermediates remained constant in darkened isolated chloroplasts, but declined rapidly in chloroplasts isolated from darkened protoplasts. When fructose 1,6-bisphosphatase was pre-activated by treating protoplasts with dithiothreitol the lag was only slightly shortened. These results are discussed in terms of control of the rate of the photosynthesis during the lag by substrates rather than limitation imposed by activity of any of the enzymes measured. 相似文献
87.
SYNOPSIS Heterotrophic (dark) CO2 fixation by Euglena gracilis strain Z varies with phase of batch culture growth and mode of nutrition. Increases in the fixation during growth cycles correlate closely with the depletion of exogenous NH4* from the medium during growth. It is demonstrated that exogenous NH4+ regulates a component of heterotrophic CO2 fixation and that another component is independent of NH4+. This is true for cells grown heterotrophically (glucose, dark), autotrophically (CO2, light) and for a permanently bleached strain (E. gracilis SB3). Some kinetics of the NH4+ regulation are presented. 相似文献
88.
One-cell rabbit zygotes were cultured at 39 degrees C in basal synthetic medium II (BSM-II) with 5%, 10%, or 15% CO2 and humidified air to determine the effect of CO2 concentration on development in vitro. After 4 days in culture, 37% of the embryos grown in 10% or 15% CO2 had reached the hatching blastocyst stage, but only 10% of the embryos were hatching when cultured under 5% CO2 (P = 0.01). Over all blastocysts, cell numbers were 207, 246, and 205 for the 5%, 10%, and 15% CO2 treatments, respectively. In a second experiment to determine if there was a beneficial effect, particularly at the blastocyst stage, of a higher concentration of CO2, embryos were cultured 4 days in either 5% or 10% CO2 or for 2 days in 5% CO2 followed by 2 days in 10% CO2. The numbers of blastomeres per embryo and embryo diameter were greater (P < 0.05) in embryos cultured continuously in 10% CO2 or in 10% CO2 only during days 3 and 4 of culture than in embryos cultured continuously in 5% CO2. In a third experiment, one-cell rabbit zygotes were cultured with 5% or 10% CO2 in a defined, protein-free medium consisting of 1:1 RPMI 1640 and Dulbecco's modified Eagle's medium. The proportion of embryos hatching and cell counts were significantly greater (P < 0.01) when cultured in the presence of 10% CO2. These data indicate that a 10% CO2 atmosphere exerts a beneficial effect on the development of zygotes into expanding and hatching rabbit blastocysts in vitro. 相似文献
89.
Marty A Chulalaksananukul W Willemot RM Condoret JS 《Biotechnology and bioengineering》1992,39(3):273-280
This study compares two solvents for enzymatic reactions: supercritical carbon dioxide (SCCO(2)) and organic solvent (n-hexane). The model reaction that was chosen was the esterification of oleic acid by ethanol catalyzed by an immobilized lipase from Mucor miehei (Lypozyme). The stability of the enzyme appeared to be quite good and similar in both media but was affected by the water content. Partition of water between solvents and immobilized enzyme has been calculated from experimental adsorption isotherms. The water content of the solid phase has a dramatic influence on the activity of the enzyme and its optimum value for activity was about 10% (w/w) in both media. A kinetic study enabled a Ping-Pong Bi-Bi reaction mechanism with inhibition by ethanol to be suggested. Despite some differences in kinetic constants, activity was in the same range in both media. Hypotheses for explaining the kinetic constant variations have been proposed and particular attention has been paid to the pH effects. 相似文献
90.
Two rice ( Oryza sativa L.) cultivars of contrasting morphologies, IR-36 and Fujiyama-5, were exposed to ambient (360 μl l−1 ) and ambient plus 300 μl l−1 CO2 from time of emergence until ca 50% grain fill at the Duke University Phytotron, Durham, North Carolina. Exposure to increased CO2 resulted in about a 50% increase in the photosynthetic rate for both cultivars and photosynthetic enhancement was still evident after 3 months of exposure to a high CO2 environment. The photosynthetic response at 5% CO2 and the response of CO2 assimilation (A) to internal CO2 (Ci ) suggest a reallocation of biochemical resources from RuBP carboxylation to RuBP regeneration. Increases in total plant biomass at elevated CO2 were approximately the same in both cultivars, although differences in allocation patterns were noted in root/shoot ratio. Differences in reproductive characteristics were also observed between cultivars at an elevated CO2 environment with a significant increase in harvest index for IR-36 but not for Fujiyama-5. Changes in carbon allocation in reproduction between these two cultivars suggest that lines of rice could be identified that would maximize reproductive output in a future high CO2 environment. 相似文献