Metal dilution effects on the spin-crossover properties of the three-dimensional coordination polymer Fe(pyrazine)[Pt(CN)4

The 1A1 left arrow over right arrow 5T2 spin transition has been investigated in the solid solutions of Fe(x)M(1-x)(pyrazine)[Pt(CN)4] (M = Ni or Co, 0 < or = x < or = 1) having a three-dimensional polynuclear structure. Both Ni and Co dilutions tend to decrease the hysteresis width and smooth the transition curves. The enthalpy (entropy) change associated with the spin transition was found to decrease from 26 kJ mol(-1) (84 J K(-1) mol(-1)) for x = 1 to 12 kJ mol(-1) (47 J K(-1) mol(-1)) for 47% Co dilution and to 15 kJ mol(-1) (54 J K(-1) mol(-1)) for 59% Ni dilution. Raman spectroscopy revealed a mixed one- and two-mode behavior in the solid solutions. For the first time, a correlation between vibrational frequencies exhibiting one-mode behavior and the entropy change, which drives the spin crossover, is established.     

Anionic polymerization and oligomerization of 4-vinyl pyridine by alkali metal methoxides

The anionic polymerization and oligomerization of 4-vinyl pyridine by methanolic alkali metal methoxides in DMSO was studied. The molecular weights increased with increasing monomer concentration and decreased with increasing methanol concentration. This fact was utilized in the preparation of oligomers. Evidence is given that initiation is an acid-base reaction. Methanol leads not only to transfer but participates in solvation of the methoxide and growing carbanions affecting the rate of reaction. The rate of reaction decreases with increasing methanol concentration.     

NMR Relaxivities of Paramagnetic Lanthanide-Containing Polyoxometalates

The current trend for ultra-high-field magnetic resonance imaging (MRI) technologies opens up new routes in clinical diagnostic imaging as well as in material imaging applications. MRI selectivity is further improved by using contrast agents (CAs), which enhance the image contrast and improve specificity by the paramagnetic relaxation enhancement (PRE) mechanism. Generally, the efficacy of a CA at a given magnetic field is measured by its longitudinal and transverse relaxivities r₁ and r₂, i.e., the longitudinal and transverse relaxation rates T₁⁻¹ and T₂⁻¹ normalized to CA concentration. However, even though basic NMR sensitivity and resolution become better in stronger fields, r₁ of classic CA generally decreases, which often causes a reduction of the image contrast. In this regard, there is a growing interest in the development of new contrast agents that would be suitable to work at higher magnetic fields. One of the strategies to increase imaging contrast at high magnetic field is to inspect other paramagnetic ions than the commonly used Gd(III)-based CAs. For lanthanides, the magnetic moment can be higher than that of the isotropic Gd(III) ion. In addition, the symmetry of electronic ground state influences the PRE properties of a compound apart from diverse correlation times. In this work, PRE of water ¹H has been investigated over a wide range of magnetic fields for aqueous solutions of the lanthanide containing polyoxometalates [Dy^III(H₂O)₄GeW₁₁O₃₉]^5– (Dy-W₁₁), [Er^III(H₂O)₃GeW₁₁O₃₉]^5– (Er-W₁₁) and [{Er^III(H₂O)(CH₃COO)(P₂W₁₇O₆₁)}₂]¹⁶⁻ (Er₂-W₃₄) over a wide range of frequencies from 20 MHz to 1.4 GHz. Their relaxivities r₁ and r₂ increase with increasing applied fields. These results indicate that the three chosen POM systems are potential candidates for contrast agents, especially at high magnetic fields.     

Solution structure of papain as studied by molecular mechanics and molecular dynamics techniques

In this paper, we report the molecular mechanics and molecular dynamics studies of the hydration of papain using the AMBER and CHARMm programs. We studied papain in an environment with minimal hydration involving only the X-ray waters and also in the hydrated environment by adding an extra 9 Å layer of water around the residues. The effect of nonbond cutoff was studied by performing minimizations with 8 Å and 15 Å nonbond cutoffs using the program AMBER. Two different solvent models—a constant dielectric and a distance-dependent dielectric—were considered. The AMBER-minimized structure and the average structure obtained from the CHARMm simulations for papain solvated with X-ray waters are presented and compared with the X-ray crystal structure results. Results of a similar comparison of the hydrated structures were also presented. The calculated root mean square deviation between the minimized structure and the X-ray structure is smaller for the hydrated system than for the system hydrated with only the X-ray waters. Results of the molecular mechanics and molecular dynamics simulations were presented for the various regions of papain. The hydration of the active site of papain and the effect of hydration on the torsional motion of the active site residues are presented. © 1996 by John Wiley & Sons, Inc.     

Effect of Silica Particle Size on Polymer Adsorption. Morphological,Energetic and Conformational Relationships

A series of six chemically treated and untreated fumed silicas with increasing particle size (ranging from the nano- to the micrometer size) was prepared. Surface areas (and morphologies) and surface energies were determined by nitrogen adsorption and inverse gas chromatography, respectively. The adsorption of a series of PDMS with different and well-defined molecular weights was studied at different polymer concentrations. Amounts of adsorbed polymer were determined by gravimetry and the energies of adsorption were assessed by flow-microcalorimetry. Results are discussed in terms of particle surface energy and morphology effects on the conformation and the inter-connectivity of adsorbed polymer molecules.     

Numerical approximations and Padé approximants for a fractional population growth model

This paper presents an efficient numerical algorithm for approximate solutions of a fractional population growth model in a closed system. The time-fractional derivative is considered in the Caputo sense. The algorithm is based on Adomian’s decomposition approach and the solutions are calculated in the form of a convergent series with easily computable components. Then the Padé approximants are effectively used in the analysis to capture the essential behavior of the population u(t) of identical individuals.     

Spectral time moment analysis of microgel structure and dynamics

The structure and dynamics of crosslinked nanoparticles (microgels) made out of hydroxypropylcellulose (HPC) polymer chains were studied using dynamic light scattering spectroscopy. The microgel light scattering spectra were found to be highly nonexponential requiring a spectral time moment analysis in which the spectra were fit to a sum of stretched exponentials. Each term offers three parameters for analysis and represents a single spectral mode. At room temperature microgel spectra reveal three modes. Two faster modes are almost diffusive and correspond to apparent sizes of 25 and 450–650 nm. The slowest mode is independent of scattering angle and is reminiscent of the slow polymer mode observed in identical non‐crosslinked polymer solutions. When solution temperature is varied from 23 to 45°C and back, the microgel undergoes a reversible volume phase transition between 40 and 45°C. According to the time‐moment analysis, above the transition temperature two faster modes collapse into one with apparent hydrodynamic radius of 100–150 nm, while the slow mode remains largely unchanged. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 771–781, 2008     

Improved image contrast with mangafodipir trisodium (MnDPDP) during MR-guided percutaneous cryosurgery of the liver

The present study was undertaken to measure the gain observed in the liver-to-tumor contrast of perioperative images when using mangafodipir trisodium, a liver-specific contrast agent, during percutaneous cryosurgery of the liver performed under the guidance of magnetic resonance images. Retrospective quantitative analyses of MR images were performed on eleven patients having a total of 30 liver tumors treated by MR-guided percutaneous cryosurgery. An initial group of four patients were treated with no contrast agent, and was compared with a second group of 7 patients who received an intravenous injection of 5 microM/kg of mangafodipir for their cryosurgery. The percutaneous cryosurgery was monitored under the near-real-time-imaging mode of a 0.5T open-configuration MRI system using a T(1)-weighted Gradient-recalled echo pulse sequence. A significant improvement in the liver-to-tumor contrast-to-noise ratio was observed with mangafodipir (p < 0.05, paired t test) in 0.5T preoperative images. Along with the stability of the mangafodipir contrast enhancement during the entire cryosurgical procedure, the resulting gain in contrast allowed for better visualizing the presence of residual untreated tumor margins at the periphery of the cryosurgery iceball directly from perioperative images acquired with patients under narcosis. Consequently, it not only became easier for the interventionalist to determine the need for an additional cryoprobe to increase the size of the iceball during the procedure, but also to decide on the appropriate end point of the cryosurgery.     

Selective photoswitching of the binuclear spin crossover compound {[Fe(bt)(NCS)2]2(bpm)} into two distinct macroscopic phases

The low-spin (LS-LS, S = 0) diamagnetic form of the binuclear spin crossover complex {[Fe(bt)(NCS)(2)](2)(bpm)} was selectively photoconverted into two distinct macroscopic phases at different excitation wavelengths (1342 or 647.1 nm). These long-lived metastable phases have been identified, respectively, as the symmetry-broken paramagnetic form (HS-LS, S = 2) and the antiferromagnetically coupled (HS-HS, S = 0) high-spin form of the compound. The selectivity may be explained by the strong coupling of the primary excited states to the paramagnetic state.     

A new experimental method for the determination of the one phonon density of states in GaAs

The one phonon density of states in GaAs is obtained from the measured disorder-activated-first-order Raman-scattering in Ga_1?xAl_xAs_x alloys. The agreement with several theoretical determinations is excellent. We discuss the requirements that, both the isoelectronic substitution and the experimental conditions must fullfil in order to apply this method to other III–V compounds.