Extension of the Coulomb–Hole–Hartree–Fock theory to molecules

The Coulomb–Hole–Hartree–Fock method introduced by E. Clementi in the early 1960s and reparametrized more recently by S. Chakraworty and E. Clementi to compute the correlated electronic energy in atomic systems, is here extended to compute molecules. The new parametrization is obtained empirically by fitting first and second atomic ionization potentials from He to Ca and a few diatomic molecules. The present formulation makes use of either one or more determinants in order to ensure proper dissociation products, following the early proposal of G.C. Lie and E. Clementi in the context of density functional computations for molecular systems. The new formulation is tested against the dissociation energies of a large number of molecules and it is found satisfactory. © 1995 John Wiley & Sons, Inc.     

Microscopic imaging of slow flow and diffusion: a pulsed field gradient stimulated echo sequence combined with turbo spin echo imaging.

In this paper we present a pulse sequence that combines a displacement-encoded stimulated echo with rapid sampling of k-space by means of turbo spin echo imaging. The stimulated echo enables the use of long observation times between the two pulsed field gradients that sample q-space completely. Propagators, constructed with long observation times, could discriminate slowly flowing protons from diffusing protons, as shown in a phantom in which a plug flow with linear velocity of 50microm/s could clearly be distinguished from stationary water. As a biological application the apparent diffusion constant in longitudinal direction of a transverse image of a maize plant stem had been measured as a function of observation time. Increasing contrast in the apparent diffusion constant image with increasing observation times were caused by differences in plant tissue: although the plant stem did not take up any water, the vascular bundles, concentrated in the outer ring of the stem, could still be discerned because of their longer unrestricted diffusional pathways for water in the longitudinal direction compared to cells in the parenchymal tissue. In the xylem region of a tomato pedicel flowing water could be distinguished from a large amount of stationary water. Linear flow velocities up to 0.67 mm/s were measured with an observation time of 180 ms.     

0.7 and 3 T MRI and Sap Flow in Intact Trees: Xylem and Phloem in Action

Dedicated magnetic resonance imaging (MRI) hardware is described that allows imaging of sap flow in intact trees with a maximal trunk diameter of 4 cm and height of several meters. This setup is used to investigate xylem and phloem flow in an intact tree quantitatively. Due to the fragile gradients in pressure present in both xylem and phloem, methods to study xylem and phloem transport must be minimally invasive. MRI flow imaging by means of this hardware certainly fulfils this condition. Flow is quantified in terms of (averaged) velocity, volume flow (flux) and flow conducting area, either in imaging mode or as a nonspatially resolved total. Results obtained for one tree, imaged at two different field strengths (0.7 and 3 T), are compared. An overall shortening of observed T ₂ values is manifest going from 0.7 to 3 T. Although some susceptibility artefacts may be present at 3 T, the results are still reliable and the gain in sensitivity results in shorter measurement time (or higher signal-to-noise ratio) with respect to the 0.7 T system. The results demonstrate that by use of dedicated hardware, xylem and phloem flow and its mutual interaction, can be studied in intact trees in relation to the water balance and in response to environmental (stress) conditions. Authors' address: Henk Van As, Laboratory of Biophysics, Wageningen University, Drejenlaan 3, 6703 HA Wageningen, The Netherlands     

Elucidating the Supramolecular Copolymerization of N- and C-Centered Benzene-1,3,5-Tricarboxamides: The Role of Parallel and Antiparallel Packing of Amide Groups in the Copolymer Microstructure

An in-depth study of the supramolecular copolymerization behavior of N- and C-centered benzene-1,3,5-tricarboxamides (N- and C-BTAs) has been conducted in methylcyclohexane and in the solid state. The connectivity of the amide groups in the BTAs differs, and mixing N- and C-BTAs results in supramolecular copolymers with a blocky microstructure in solution. The blocky microstructure results from the formation of weaker and less organized, antiparallel hydrogen bonds between N- and C-BTAs. In methylcyclohexane, the helical threefold hydrogen-bonding network present in C- and N-BTAs is retained in the mixtures. In the solid state, in contrast, the hydrogen bonds of pure BTAs as well as their mixtures organize in a sheet-like pattern, and in the mixtures long-range order is lost. Drop-casting to kinetically trap the solution microstructures shows that C-BTAs retain the helical hydrogen bonds, but N-BTAs immediately adopt the sheet-like pattern, a direct consequence of the lower stabilization energy of the helical hydrogen bonds. In the copolymers, the stability of the helical aggregates depends on the copolymer composition, and helical aggregates are only preserved when a high amount of C-BTAs is present. The method outlined here is generally applicable to elucidate the copolymerization behavior of supramolecular monomers both in solution as well as in the solid state.     

Normal-incidence reflectance of optimized W /B(4) C x-ray multilayers in the range 1.4 nm < l > 2.4 nm

We have fabricated W/B(4)C multilayers having periods in the range d = 0.8-1.2 nm and measured their soft-x-ray performance near normal incidence in the wavelength range 1.4相似文献   

Observation of two-magnon bound states in the two-leg ladders of (Ca,La)(14)Cu(24)O(41)

Phonon-assisted two-magnon absorption is studied in the spin- 1/2 two-leg ladders of (Ca,La)(14)Cu(24)O(41) for E parallel c (legs) and E parallel a (rungs). We verify the theoretically predicted existence of two-magnon singlet bound states, which give rise to peaks at approximately equal to 2140 and 2800 cm(-1). The two-magnon continuum is observed at approximately equal to 4000 cm(-1). Two different theoretical approaches (Jordan-Wigner fermions and perturbation theory) describe the data very well for J parallel approximately equal to 1020-1100 cm(-1), J parallel/J perpendicular approximately equal to 1-1.2. At high energies, the magnetic contribution to sigma(omega) is strikingly similar in the ladders and in the undoped high-T(c) cuprates, which emphasizes the importance of strong quantum fluctuations in the latter.     

Ring enlargement reactions of tetramic acid derivatives

The 4‐hydroxypyridones 7 and 3‐hydroxypyridones 8/9 (azagrevellins) were prepared by reaction of the pyrrolidinetrione 4 and diazoalkanes. The ring enlargement proceeded by anionotropic [1,2]‐rearrangement introducing carbon between C‐3 and C‐4 or, to a lesser extent, between C‐2 and C‐3 due to the different migration aptitudes of the two acyl groups involved. In a cognate manner ring expansion between C‐2 and C‐3 occured by the interaction of diazomethane and the pyrrolidinetrione hydrazone 15 , to give the spiroe‐poxide 16 as the final product. From the reaction of trione 4 and diazomethane, however, the diepoxide 14 was obtained. In this case ring homologation must have taken place by insertion of carbon between C‐4 and C‐5. In a two step ring expansion the pyridones 21 and 22 were obtained from the maleineimides 17.     

A portable Halbach magnet that can be opened and closed without force: the NMR-CUFF

Portable equipment for nuclear magnetic resonance (NMR) is becoming increasingly attractive for use in a variety of applications. One of the main scientific challenges in making NMR portable is the design of light-weight magnets that possess a strong and homogeneous field. Existing NMR magnets can provide such magnetic fields, but only for small samples or in small regions, or are rather heavy. Here we show a simple yet elegant concept for a Halbach-type permanent magnet ring, which can be opened and closed with minimal mechanical force. An analytical solution for an ideal Halbach magnet shows that the magnetic forces cancel if the structure is opened at an angle of 35.3° relative to its poles. A first prototype weighed only 3.1 kg, and provided a flux density of 0.57 T with a homogeneity better than 200 ppm over a spherical volume of 5mm in diameter without shimming. The force needed to close it was found to be about 20 N. As a demonstration, intact plants were imaged and water (xylem) flow measured. Magnets of this type (NMR-CUFF = Cut-open, Uniform, Force Free) are ideal for portable use and are eminently suited to investigate small or slender objects that are part of a larger or immobile whole, such as branches on a tree, growing fruit on a plant, or non-metallic tubing in industrial installations. This new concept in permanent-magnet design enables the construction of openable, yet strong and homogeneous magnets, which aside from use in NMR or MRI could also be of interest for applications in accelerators, motors, or magnetic bearings.     

Normal-incidence silicon-gadolinium multilayers for imaging at 63 nm wavelength

Si/Gd multilayers designed as narrowband reflective coatings near 63 nm were developed. The highest peak reflectance of 26.2% at a 5 degrees incident angle was obtained at 62 nm, and the spectral bandwidth was 7.3 nm FWHM. The fits for x-ray and extreme ultraviolet reflectance data of Si/Gd multilayers indicate the possibility of silicide formation at the Si-Gd interfaces. B(4)C, W, and SiN were deposited as interface barrier layers to improve the reflectance of Si/Gd multilayers. More than an 8% increase in reflectance was observed from the interface-engineered Si/W/Gd and Si/B(4)C/Gd multilayers.     

Automatization for development of HPLC methods

Within the frame of inprocess analytics of the synthesis of pharmaceutical drugs a lot of HPLC methods are required for checking the quality of intermediates and drug substances. The methods have to be developed in terms of optimal selectivity and low limit of detection, minimum running time and chromatographic robustness. The goal was to shorten the method development process. Therefore, the screening of stationary phases was automated by means of switching modules equipped with 12 HPLC columns. Mobile phase and temperature could be optimized by using Drylab after evaluating chromatograms of gradient elutions performed automatically. The column switching module was applied for more than three dozens of substances, e.g. steroidal intermediates. Resolution (especially of isomeres), peak shape and number of peaks turned out to be the criteria for selection of the appropriate stationary phase. On the basis of the "best" column the composition of the "best" eluent was usually defined rapidly and with less effort. This approach leads to savings in manpower by more than one third. Overnight, impurity profiles of the intermediates were obtained yielding robust HPLC methods with high selectivity and minimized elution time.