Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.

A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins.     

Substituent control of hydrogen bonding in palladium(II)-pyrazole complexes

Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions.     

Synthetic protocols and building blocks for molecular electronics

Simple and readily accessible aryl bromides are useful building blocks for thiol end-capped molecular wires. Thus, 4-bromophenyl tert-butyl sulfide and 1-bromo-4-(methoxymethyl)benzene serve as precursors for a variety of oligo(phenylenevinylene) and oligo(phenyleneethynylene) wires via efficient synthetic transformations as presented in this paper.     

Fixed points and matching points in partitions

The Ramanujan Journal - We study fixed points in integer partitions viewed, respectively, as weakly increasing or weakly decreasing structures. A fixed point is a point with value i in position i....     

On the use of Helmholtz resonators as sound attenuators

Summary In the present paper a nonlinear acoustic theory is proposed, to accurately describe the properties of a generalized type of Helmholtz resonators. The theory may be used as a layout tool to design sound attenuators for combustion facilities. The present investigation shows that, in addition to the nonlinear effects, the effects due to thermoacoustic boundary layers and the first frequency correction to the Helmholtz approximation should be taken into account, in order to predict the frequency-dependent attenuation properties of Helmholtz attenuators with the accuracy required by typical technical applications. A series of experiments is presented which is used to validate the theoretical predictions.

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Zusammenfassung In der vorliegenden Abhandlung wird eine nichtlineare akustische Theorie vorgeschlagen, mit der das Verhalten einer verallgemeinerten Art von Helmholtzresonatoren beschrieben werden kann. Die Theorie kann als Werkzeug zur Auslegung von Schalldämpfern für Verbrennungsanlagen benutzt werden. Die vorliegende Arbeit zeigt, dass neben den nichtlinearen Effekten auch die Einflüsse der thermoakustischen Grenzschichten und der ersten Frequenzkorrektur zur Helmholtzapproximation berücksichtigt werden müssen, damit die frequenzabhängigen Eigenschaften von Helmholtzdämpfern mit technisch ausreichender Genauigkeit beschrieben werden können. Mit einer Reihe von Experimenten werden die theoretischen Ergebnisse untermauert.

     

Der Systembegriff der Kontrolltheorie und Regel-Relative

To characterize E. D. Sontag’s system of axioms for control-systems in a more operative manner we consider an equivalent algebraic structure, which we name Regel- Relative.     

A perturbative approach toB decays into two π mesons

The modified perturbative approach in which transverse degrees of freedom as well as Sudakov suppressions are taken into account, is applied toB decays into two mesons. The influence of various model parameters (CKM) matrix elements,B decay constant, mesonic wave functions) on the results as well as short distance corrections to the weak Hamiltonian are discussed in some detail. The perturbative contributions to theB decays yield branching ratios of the order of 10^–7–10^–6 which values are well below the upper limit for the branching ratio as measured by CLEO.Supported by the Deutsche Forschungsgemeinschaft     

Asymptotics of heavy atoms in high magnetic fields: II. Semiclassical regions

The ground state energy of an atom of nuclear chargeZe in a magnetic fieldB is exactly evaluated to leading order asZ in the following three regions:BZ ^4/3,BZ ^4/3 andZ ^4/3BZ³. In each case this is accomplished by a modified Thomas-Fermi (TF) type theory. We also analyze these TF theories in detail, one of their consequences being the nonintuitive fact that atoms are spherical (to leading order) despite the leading order change in energy due to theB field. This paper complements and completes our earlier analysis [1], which was primarily devoted to the regionsBZ ³ andBZ³ in which a semiclassical TF analysis is numerically and conceptually wrong. There are two main mathematical results in this paper, needed for the proof of the exactitude of the TF theories. One is a generalization of the Lieb-Thirring inequality for sums of eigenvalues to include magnetic fields. The second is a semiclassical asymptotic formula for sums of eigenvalues that isuniform in the fieldB.Work partially supported by U.S. National Science Foundation grant PHY90-19433 A02Work partially supported by U.S. National Science Foundation grant DMS 92-03829Work partially supported by the Heraeus Stiftung and the Research Fund of the University of Iceland.