Molecular dynamics and information on possible sites of interaction of intramyocellular metabolites in vivo from resolved dipolar couplings in localized H NMR spectra

Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl-l-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct ¹H–¹H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized ¹H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD₀ (S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 (δ = 8 ppm) and H4 (δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD₀ from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution ¹H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D₀ (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 − 3) × 10⁻⁴ indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 − 137) × 10⁻⁴. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, ¹H NMR experiments on aqueous model solutions of histidine and N-acetyl-l-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo ¹H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle (θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids.     

Photorefractive Four-Wave Mixing Switches Utilizing Pockels Effect -Longitudinal and Lateral Switches-

We carried out detailed calculations for photorefractive wave-mixing switches based on one of three crystals with high electro-optic coefficients, namely, BaTiO₃, Strontium Barium Niobate (SBN (0.75)), and Potasium Sodium Strontium Barium Niobate (KNSBN). A comparison of results for the three crystals shows that a 0_-cut BaTiO³ crystal is suitable for a longitudinal switch and requires a voltage of about 80 for a 2-mm-thick crystal to induce sufficient phase mismatch. The electrodes must be transparent for the incident and diffracted beams. A 45_-cut SBN (0.75) crystal, however, is suitable for a lateral switch and requires a voltage of about 150 for a 1-mm-wide crystal. The electrodes do not need to be transparent.     

Color Zone Map in Peripheral Vision at Various Illuminance Levels

We measured the entire region of mesopic and photopic vision to determine the color zone covering the visual field with unique red, yellow, green, and blue hue components. Eight kinds of test stimuli in the natural color system (NCS) color notation system were used. These stimuli were presented at horizontal and vertical meridians, and at meridians inclined at 45° angles. The illuminance level was set at six levels: 0.01 lx-1000 lx. The evaluation method measured chromatic, white, and black components as well as the hue component of the stimuli. Results show that the color zone of the retina extended further into the periphery with increasing illuminance; the response of opponent colors y-b was shown to be greater than that of the opponent colors r-g.     

A realistic coronary artery phantom for particle image velocimetry

Myocardial infarction results from the rupture of an atherosclerotic plaque, which occurs in response to both mechanical stress and inflammatory processes. In order experimentally observe flow into atherosclerotic coronary artery morphologies, a novel technique for molding realistic compliant phantom featuring injection-molded inclusions and multiple layers has been developed. This transparent phantom allows for particle image velocimetry (PIV) flow analysis and can supply experimental data to validate computational fluid dynamics algorithms and hypothesis.     

Real-time color holographic interferometry devoted to 2D unsteady wake flows

A new optical technique based on real time holographic interferometry in true colors has been implemented around the transonic wind tunnel of the ONERA-Lille center to analyze 2D unsteady wake flows. Tests realized in color interferometry, real time and double exposure, use simultaneously three wavelengths of a continuous waves laser (argon and krypton mixed) and holograms are recorded on silver-halide single-layer panchromatic Slavich PFG03c plates. The very principle of real-time true color holographic interferometry uses three primary wavelengths (red, green and blue) to record, under no-flow conditions, the interference among the three measurement beams and the three reference beams simultaneously on a single reference hologram. After the holographic plate is developed, it is placed on the test setup again in the position it occupied during exposure and the hologram is illuminated again by the three reference beams and three measurement beams. A flat, uniform color can then be observed behind the hologram. So a horizontal, vertical, or even circular fringe pattern can be formed and the achromatic central fringe can be made out very clearly. The single color is used to determine the path difference zero on the interferograms. The flow studied was the unsteady flow downstream of a cylinder placed crosswise in the test section. A sequence of hundred interferograms was recorded on the flow around the cylinder at Mach 0.37. The vortex formation and dissipation phases can be seen very clearly, along with the fringe beat to either side of the cylinder.     

New 7‐membered diazepanone alkoxyamines for nitroxide‐mediated radical polymerization

The synthesis of new 7‐membered diazepanone alkoxyamines [2,2,7,7‐tetramethyl‐1‐(1‐phenyl‐ethoxy)‐[1,4]diazepan‐5‐one ( 3 ) and 2,7‐diethyl‐2,3,7‐trimethyl‐1‐(1‐phenyl‐ethoxy)‐[1,4]diazepan‐5‐one ( 8 )] through the Beckmann rearrangement of piperidin‐4‐one alkoxyamines was developed. Both 3 and 8 were evaluated as initiators and regulators for the nitroxide‐mediated radical polymerization of styrene and n‐butyl acrylate. 8 , a sterically highly hindered alkoxyamine readily available as a crystalline solid, allowed the fast and controlled polymerization and preparation of polymers with low polydispersity indices (1.2–1.4) up to a degree of polymerization of about 100. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3332–3341, 2004     

Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

Enlightened sonochemistry

Sonochemistry and photochemistry are initiated by high-energy transient species, which may be prone to mutual interaction. Electronic excitation of solutes by energy transfer from high energy species generated in collapsing bubbles is already supported by experimental evidence. The rates of photochemical reactions can be affected by ultrasound-induced mixing of liquids caused by microstreaming near pulsating cavitation bubbles and shockwaves due to bubble collapse. This may not only improve light absorption but also modify the pathway of reaction by increasing the contact between reagents. Finally, one may speculate about a potentially new chemistry of photoexcited solutes under the extreme conditions inside cavitation microreactors. This work reviews research on the excitation of solutes by sonoluminescence, the combined effects of ultrasound and light on liquid systems and the effect of ultrasound on photocatalytic reactions.     

The combinatorics of the bar resolution in group cohomology

We study a combinatorially defined double complex structure on the ordered chains of any simplicial complex. Its columns are related to the cell complex K_n whose face poset is isomorphic to the subword ordering on words without repetition from an alphabet of size n. This complex is shellable and as an application we give a representation theoretic interpretation for derangement numbers and a related symmetric function considered by Désarménien and Wachs [11].

We analyze the two spectral sequences arising from the double complex in the case of the bar resolution for a group. This spectral sequence converges to the cohomology of the group and provides a method for computing group cohomology in terms of the cohomology of subgroups. Its behavior is influenced by the complex of oriented chains of the simplicial complex of finite subsets of the group, and we examine the Ext class of this complex.