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11.
A perturbative approach is employed to solve the Bloch-Torrey equations in the presence of distant-dipole fields in nuclear magnetic resonance. The procedure, although only carried out to first order in the perturbation parameter a=1/k2Dtaud, could, in principle, be generalized to higher orders. Here D is the diffusivity, taud the dipolar demagnetization time, and k is the wave vector of the spatial modulation of magnetization produced by the magnetic field gradient. The results are especially interesting for dilute binary mixtures consisting of molecular species with different diffusivities. In this case the calculated two-dimensional correlation spectroscopy revamped by asymmetric Z-gradient echo detection spectra are shown to be free from some inadequacies resulting from a simplistic application of standard approximations. 相似文献
12.
Laser flash absorption spectroscopy has been used to investigate the kinetics of electron transfer from P700 in Photosystem I (PSI)-enriched particles from spinach to the ferredoxins from spinach and the green alga Monoraphidium braunii. Very similar behavior for the interaction of both ferredoxins with the PSI complex was observed, although the algal ferredoxin appears to be slightly more effective as an electron acceptor. For both proteins, a non-linear protein concentration dependence of the rate constant for reduction was obtained, indicating complex formation preceding electron transfer. Estimates of 3 times 107M?1 s?1 and 140–180 s?l were obtained from these data for the second order rate constants for complex formation, and the limiting first order rate constants for electron transfer, respectively. At neutral pH, a biphasic dependence of the rate constant for ferredoxin reduction on the concentration of NaCl or MgCl2 was observed. This was interpreted in terms of the electrostatic interactions which occur between ferredoxin and the PSI membrane. In addition, magnesium cations appear to play a specific role in the interaction between PSI and ferredoxin. Thus, the addition of these ions under optimal conditions induces a 6-f-old increase in the electron transfer reaction rate constant, compared with a 2-f-old increase in the presence of an optimal amount of NaCI. This cannot be explained as arising from ionic strength effects. To our knowledge, this is the first time that a direct measurement of the rate constant for the reduction of ferredoxin by the PSI complex has been reported. 相似文献
13.
Manuel A. Fernandes Marcus Layh Bernard Omondi 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):o384-o385
The title compound, C10H11N, displays a crystallographic mirror plane that incorporates all the non‐H atoms, as well as the H atoms attached to the aromatic ring. The isocyano group is almost linear and shows an N[triple‐bond]C bond distance of 1.158 (3) Å. 相似文献
14.
Braulio Insuasty Jairo Quiroga Juan Carlos Argoti Samuel Gmez Roberto Martínez Enrique Angeles Rubn Gabio Manuel Nogueras Adolfo Snchez 《Journal of heterocyclic chemistry》1998,35(6):1397-1399
The reaction of 1-aryl-3-(dimethylamino)-1-propanones 1 with one equivalent of 4,5-diamino-1H-pyrimidin-6-ones 2 , in acidic medium, leads to the formation of 4-aryl-2,3,6,7-tetrahydro-1H-pyrimido[4,5-b]-[1,4]diazepin-6-ones 3 . The structure elucidation of the products is based on detail nmr analysis of experiments such as 13C, 1H and DEPT including selective 13C{1H} decoupling experiments. 相似文献
15.
The present work proposes a new approach for the evaluation of the information content in latent variables, and therefore, for the determination of the regression model dimensionality. Several examples are provided, using simulated, real-world, and reference datasets. The results showed that the application of the Durbin-Watson (DW) criterion could be used for the determination of the number of latent variables. Moreover, the method is straightforward in its implementation and could help in the understanding of model behaviour, particularly in complex datasets. A comparison is made with cross-validation techniques for the case of reference datasets, showing the potential of the Durbin-Watson criterion in the characterisation of the regression model. The advantages and disadvantages of this procedure (compared to cross-validation) are discussed. The properties of the information content of the regression vectors (loadings p, w and b vectors) are shown as well as how to use them for the current purpose. 相似文献
16.
The treatment of polybutadienes with iron carbonyls results in formation of polymers containing tricarbonyl(conjugated diene)iron units [C8H12Fe(CO)3] and also results in geometrical isomerization of free double bonds. Heating of the iron carbonyl-containing polymers gives ferromagnetic products with enhanced thermal stability. The incorporation of iron carbonyl groups into the polymer is favored by basic solvents and high temperatures, the geometrical isomerization by acidic solvents and low temperatures. Steric factors are powerful in determining the rate of isomerization. 相似文献
17.
The metal binding properties of the dinucleotide duplex, dCG x dCG, were analyzed in the gas phase with ion mobility mass spectrometry. Both MALDI and ESI were used to generate [M(dCG x dCG)]+ complexes. The collision cross section of each complex was measured in helium using ion mobility based methods and compared to calculated cross sections of theoretical structures. When metal cations classified as hard acids were combined with dCG x dCG, the [M(dCG x dCG)]+ complex organized into a globular structure. However, when soft acid metal cations were examined, a structure was observed where the two C-G base pairs were Watson-Crick bound. 相似文献
18.
A kinetic method is presented for the determination of 0.5–5 μg ml?1 gallium based on its activating effect on the copper(II)-catalyzed oxidation of 4,4′-dihydroxybenzophenone thiosemicarbazone by hydrogen peroxide. The reaction is monitored spectrophotometrically at 415 nm. Two sets of reaction conditions are established; one for the direct determination of gallium, and another, in which indium affects the gallium response, for determination of indium. Mixtures of these cations can be determined at μg ml?1 levels and in gallium/indium ratios from 7.5:1 to 1:1.6, with an accuracy and precision of ca. 4.5%. 相似文献
19.
Manuel Valdivia 《manuscripta mathematica》1979,26(4):381-386
In [1] Tukey proves that if A and B are closed convex subsets in a Banach space, so that A is bounded and A-B is dense in the open unit ball U then A-BU. We shall give here a more general result than the former one which contains the Banach's isomorphism theorem as particular case. Other results over convex sets are also given.The author is indebted to the referee for the several very valuable comments. 相似文献
20.
Aimee A. Sanford Brea A. Manuel Misael A. Romero-Reyes Jennifer M. Heemstra 《Chemical science》2022,13(26):7670
Small molecule contaminants pose a significant threat to the environment and human health. While regulations are in place for allowed limits in many countries, detection and remediation of contaminants in more resource-limited settings and everyday environmental sources remains a challenge. Functional nucleic acids, including aptamers and DNA enzymes, have emerged as powerful options for addressing this challenge due to their ability to non-covalently interact with small molecule targets. The goal of this perspective is to outline recent efforts toward the selection of aptamers for small molecules and describe their subsequent implementation for environmental applications. Finally, we provide an outlook that addresses barriers that hinder these technologies from being widely adopted in field friendly settings and propose a path forward toward addressing these challenges.Small molecule contaminants pose a significant threat to the environment and human health. 相似文献