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1.
EQCM and voltammetric data show that thallium(I) ions, which are adsorbed in the region of the positive surface charge, most probably, in the form of the ionic pairs, are not reduced. In this potential region, thallium(I) ions are reduced directly from the solution. At more negative potentials, the previously adsorbed stable ionic pairs slowly undergo transition into the less stable form. From this form, thallium(I) ions can be reduced or desorbed into the solution. The process is best described by a model of one electron, i.e., full charge transfer.  相似文献   
2.
The Crank–Nicolson (CN) simulation method has an oscillatory response to sharp initial transients. The technique is convenient but the oscillations make it less popular. Several ways of damping the oscillations in two types of electrochemical computations are investigated. For a simple one-dimensional system with an initial singularity, subdivision of the first time interval into a number of equal subintervals (the Pearson method) works rather well, and so does division with exponentially increasing subintervals, where however an optimum expansion parameter must be found. This method can be computationally more expensive with some systems. The simple device of starting with one backward implicit (BI, or Laasonen) step does damp the oscillations, but not always sufficiently. For electrochemical microdisk simulations which are two-dimensional in space and using CN, the use of a first BI step is much more effective and is recommended. Division into subintervals is also effective, and again, both the Pearson method and exponentially increasing subintervals methods are effective here. Exponentially increasing subintervals are often considerably more expensive computationally. Expanding intervals over the whole simulation period, although capable of satisfactory results, for most systems will require more cpu time compared with subdivision of the first interval only.  相似文献   
3.
The photocontrol of anthocyanin synthesis in dark-grown seedlings of tomato (Lycopersicon esculentum Mill.) has been studied in an aurea (au) mutant which is deficient in the labile type of phytochrome, a high pigment (hp) mutant which has the wild-type level of phytochrome and the double mutant au/hp , as well as the wild type. The hp mutant demonstrates phytochrome control of anthocyanin synthesis in response to a single red light (RL) pulse, whereas there is no measurable response in the wild type and au mutant. After pretreatment with 12 h blue light (BL) the phytochrome regulation of anthocyanin synthesis is 10-fold higher in the hp mutant than in the wild type, whilst no anthocyanin is detectable in the au mutant, thus suggesting that it is the labile pool of phytochrome which regulates anthocyanin synthesis. The au/hp double mutant exhibits a small (3% of that in the hp mutant) RL/far-red light (FR)-reversible regulation of anthocyanin synthesis following a BL pretreatment. It is proposed that the hp mutant is hypersensitive to the FR-absorbing form of phytochrome (Pfr) and that this (hypersensitivity) establishes response to the low level of Pfl. (below detection limits in phytochrome assays) in the au/hp double mutant.  相似文献   
4.
Methylene blue transfers electrons to a membrane-associated b-type cytochrome in particulate fractions from corn coleoptiles. The Km for methylene blue is less than 1 µM under optimal conditions. This reaction is destroyed by boiling, but not by 7 M urea. Kinetic analyses of the influence of light intensity on cytochrome reduction suggest that a first order photochemical reaction is limiting. Free EDTA may serve as an electron donor in this system at least at high methylene blue and protein concentrations. The photoactivity does not coincide either with mitochondrial or endoplasmic reticulum markers, and may be localized in plasma membrane. There is an estimated 5 times 10-10 mol photoreducible cytochrome per g coleoptile tissue. Studies on the effect of pH on the reaction in the presence of methylene blue or thionine indicate that dye photoreduction itself is not rate-limiting. Wavelength dependence studies suggest that it is methylene blue monomer and not dimer which mediates the reaction. Although oxygen is apparently required for the reaction, neither superoxide nor excited singlet oxygen appear to be involved. The reaction mechanism is still unknown.  相似文献   
5.
A collaborative study on the robustness and portability of a capillary electrophoresis‐mass spectrometry method for peptide mapping was performed by an international team, consisting of 13 independent laboratories from academia and industry. All participants used the same batch of samples, reagents and coated capillaries to run their assays, whereas they utilized the capillary electrophoresis‐mass spectrometry equipment available in their laboratories. The equipment used varied in model, type and instrument manufacturer. Furthermore, different types of sheath‐flow capillary electrophoresis–mass spectrometry interfaces were used. Migration time, peak height and peak area of ten representative target peptides of trypsin‐digested bovine serum albumin were determined by every laboratory on two consecutive days. The data were critically evaluated to identify outliers and final values for means, repeatability (precision within a laboratory) and reproducibility (precision between laboratories) were established. For relative migration time the repeatability was between 0.05 and 0.18% RSD and the reproducibility between 0.14 and 1.3% RSD. For relative peak area repeatability and reproducibility values obtained were 3–12 and 9–29% RSD, respectively. These results demonstrate that capillary electrophoresis‐mass spectrometry is robust enough to allow a method transfer across multiple laboratories and should promote a more widespread use of peptide mapping and other capillary electrophoresis‐mass spectrometry applications in biopharmaceutical analysis and related fields.  相似文献   
6.
An important historical paper on the numerical solution of pde's has regularly, but incorrectly, been assigned to the year 1951. The origin of this error of reference is discussed.  相似文献   
7.
The like-sign dimuons copiously recorded in the NA 38 experiment both inp-U and O?U reactions at 200 GeV/nucleon are interpreted as resulting from decays of π andK mesons in comparable proportions. The ++/?? ratio is large (?1.7) and ascribed to theK + being more copiously produced than theK ?. Both the average transverse momentum and the ++/?? ratio are comparable forp-U and O?U reactions, and both increase only slightly with the transverse energyE T .  相似文献   
8.
9.
The endohedral fullerene epoxide N@C60O was synthesised, isolated by High Performance Liquid Chromatography (HPLC), and characterised by Electron Spin Resonance (ESR). This nitrogen radical displays predominantly axial symmetry characteristics as expected for a monoadduct, evidenced by a zero-field splitting D parameter of 6.6 MHz and an E parameter of 0.5 MHz in powder at 77 K. Photo- and thermally-activated silencing of the nitrogen radical were observed, the latter showing the evolution of a new spin signal during heating at 100 degrees C. We suggest that loss of nitrogen spin is due to coupling with a radical formed by opening of the epoxide ring. This implies that the reaction of C60O with C60 in the solid state proceeds via a radical, rather than ionic, intermediate.  相似文献   
10.
The Crank-Nicolson (CN) simulation method has an oscillatory response to sharp initial transients. The technique is convenient but the oscillations make it less popular. Several ways of damping the oscillations in two types of electrochemical computations are investigated. For a simple one-dimensional system with an initial singularity, subdivision of the first time interval into a number of equal subintervals (the Pearson method) works rather well, and so does division with exponentially increasing subintervals, where however an optimum expansion parameter must be found. This method can be computationally more expensive with some systems. The simple device of starting with one backward implicit (BI, or Laasonen) step does damp the oscillations, but not always sufficiently. For electrochemical microdisk simulations which are two-dimensional in space and using CN, the use of a first BI step is much more effective and is recommended. Division into subintervals is also effective, and again, both the Pearson method and exponentially increasing subintervals methods are effective here. Exponentially increasing subintervals are often considerably more expensive computationally. Expanding intervals over the whole simulation period, although capable of satisfactory results, for most systems will require more cpu time compared with subdivision of the first interval only.  相似文献   
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