N-Heterocycle (tetrazole)-stabilized pseudocyclic λ3-iodane: Synthesis and reactivity

An N-heterocycle (tetrazole)-stabilized pseudocyclic λ³-iodane was synthesized and its thermal stability and redox activity were studied. Simultaneous thermogravimetric analysis and differential scanning calorimetry revealed that the polyvalent iodine compound started to degrade at 127 °C and showed a notable exothermic decomposition peak at 147 °C, which was markedly more pronounced than the parent tetrazole with monovalent iodine. The reduction potential was determined by cyclic voltammetry to be ?0.38 V vs AgNO₃|Ag in dimethyl sulfoxide at a scan rate of 0.02 V/s. The oxidative power of the polyvalent iodine compound was demonstrated by conducting oxidation of thioanisole to sulfoxide and oxidative dimerization of thiobenzamide to 3,5-diphenyl-1,2,4-thiadiazole.     

Determination of equilibrium constants for atom transfer radical polymerization

Atom transfer radical polymerization (ATRP) equilibrium constants (K(ATRP)) were determined using modified Fischer's equations for the persistent radical effect. The original Fischer's equations could be used only for low conversion of Cu(I) to X-Cu(II) and consequently for relatively low values of K(ATRP). At higher conversion to X-Cu(II) (>10%) and for larger values of K(ATRP) (>10(-)(7)), modified equations that take into account the changes in catalyst and initiator concentrations should be used. The validity of new equations was confirmed by detailed kinetic simulations. UV-vis spectrometric and GC measurements were used to follow the evolution of X-Cu(II) species and the initiator concentration, respectively, and to successfully determine values of K(ATRP) for several catalysts and alkyl halides. The effect of structure on reactivities of ATRP components is presented.     

Low frequency rhythms in human DNA sequences: a key to the organization of gene location and orientation?

We explore large-scale nucleotide compositional fluctuations of the human genome using multiresolution techniques. Analysis of the GC content and of the AT and GC skews reveals the existence of rhythms with two main periods of 110+/-20 kb and 400+/-50 kb that enlighten a remarkable cooperative gene organization. We show that the observed nonlinear oscillations are likely to display all the characteristic features of chaotic strange attractors which suggests a very attractive deterministic picture: gene orientation and location, in relation with the structure and dynamics of chromatin, might be governed by a low-dimensional nonlinear dynamical system.     

MRI of hip prostheses using single-point methods: in vitro studies towards the artifact-free imaging of individuals with metal implants

Use of magnetic resonance imaging (MRI) in individuals with orthopedic implants is limited because of the large distortions caused by metallic components. As a possible solution for this problem, we suggest the use of single-point imaging (SPI) methods, which are immune to the susceptibility artifacts observed with conventional MRI methods. A further advantage of SPI, based on the fact that signal encoding is achieved in ultra-short times (as short as tens of microseconds), is that they enable the direct visualization of the polymeric elements of the implants, allowing the detection of possible implant failures. We present in vitro SPI images of polymeric sockets of two hip prostheses together with artifact-free images of gelatin phantoms containing their respective metallic stems. These data underscore the great potential of the SPI technique for obtaining artifact-free images of individuals with large metal implants.     

Temperature dependence of the Kondo resonance and its satellites in CeCu2Si2

We present high-resolution photoemission spectroscopy studies on the Kondo resonance of the strongly correlated Ce system CeCu2Si2. By exploiting the thermal broadening of the Fermi edge we analyze position, spectral weight, and temperature dependence of the low-energy 4f spectral features, whose major weight lies above the Fermi level E(F). We also present theoretical predictions based on the single-impurity Anderson model using an extended noncrossing approximation, including all spin-orbit and crystal field splittings of the 4f states. The excellent agreement between theory and experiment provides strong evidence that the spectral properties of CeCu2Si2 can be described by single-impurity Kondo physics down to T approximately 5 K.     

Intrinsic Josephson junctions in Bi2Sr2CaCu2O8+δ single crystals

We report on thec-axis superconducting energy gap parameter Δ _c (T) of intrinsic Josephson tunnel junctions inBi ₂ Sr ₂ CaCu ₂ O _8+δ (Bi2212) single crystals. Δ _c (4.2K)≈10−13 meV, which is approximately a factor of two smaller than reported in the majority of tunneling experiments. Δ _c (T) deviates strongly from the BCS temperature dependence. These observations may be explained by a multilayer model of Bi2212 which assumes that theBi−O layers are superconducting due to the proximity effects. The Josephson tunneling then takes place between adjacentBi−O layers while there is a strong proximity coupling betweenBi−O andCu−O layers. The work is supported by Swedish Supercon-ductivity Consortium and NUTEK, and, in part, by Russian Foundation for Basic Research, grant #95-02-04307     

On the importance of exchangeable NH protons in creatine for the magnetic coupling of creatine methyl protons in skeletal muscle

The methyl protons of creatine in skeletal muscle exhibit a strong off-resonance magnetization transfer effect. The mechanism of this process is unknown. We previously hypothesized that the exchangeable amide/amino protons of creatine might be involved. To test this the characteristics of the creatine magnetization transfer effect were investigated in excised rat hindleg skeletal muscle that was equilibrated in either H2O or D2O solutions containing creatine. The efficiency of off-resonance magnetization transfer to the protons of mobile creatine in excised muscle was similar to that previously reported in intact muscle in vivo. Equilibrating the isolated muscle in D2O solution had no effect on the magnetic coupling to the immobile protons. It is concluded that exchangeable protons play a negligible role in the magnetic coupling of creatine methyl protons in muscle.     

Two-voxel localization sequence for in vivo two-dimensional homonuclear correlation spectroscopy

The combination of localized 2D 1H MR correlation spectroscopy and Hadamard encoding allows the simultaneous acquisition of multiple volumes of interest without an increase in the experimental duration, compared to single-voxel acquisition. In the present study, 2D correlation spectra were acquired simultaneously within 20 to 40 min in two voxels located in each hemisphere of the rat brain. An intervoxel distance of 20% of the voxel size was sufficient to limit spatial contamination. The following cerebral metabolites gave detectable crosspeaks: N-acetylaspartate, the glutamate/glutamine pool, aspartate, phosphoethanolamine, glucose, glutathione, taurine, myo-inositols, lactate, threonine, gamma-aminobutyric acid, and alanine. Most of the metabolites were measured without contamination of other resonances.     

Orthogonal gas sensor arrays by chemoresistive material design

Gas sensor arrays often lack discrimination power to different analytes and robustness to interferants, limiting their success outside of research laboratories. This is primarily due to the widely sensitive (thus weakly-selective) nature of the constituent sensors. Here, the effect of orthogonality on array accuracy and precision by selective sensor design is investigated. Therefore, arrays of (2–5) selective and non-selective sensors are formed by systematically altering array size and composition. Their performance is evaluated with 60 random combinations of ammonia, acetone and ethanol at ppb to low ppm concentrations. Best analyte predictions with high coefficients of determination (R²) of 0.96 for ammonia, 0.99 for acetone and 0.88 for ethanol are obtained with an array featuring high degree of orthogonality. This is achieved by using distinctly selective sensors (Si:MoO₃ for ammonia and Si:WO₃ for acetone together with Si:SnO₂) that improve discrimination power and stability of the regression coefficients. On the other hand, arrays with collinear sensors (Pd:SnO₂, Pt:SnO₂ and Si:SnO₂) hardly improve gas predictions having R² of 0.01, 0.86 and 0.28 for ammonia, acetone and ethanol, respectively. Sometimes they even exhibited lower coefficient of determination than single sensors as a Si:MoO₃ sensor alone predicts ammonia better with a R² of 0.68.

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Graphical abstract Conventional arrays (red) with weakly-selective sensors span a significantly smaller volume in the analyte space than arrays containing distinctly-selective sensors (orthogonal array, green). Orthogonal arrays feature better accuracy and precision than conventional arrays in mixtures of ammonia, acetone and ethanol.

     

Unprecedented stereoselective synthesis of cyclopenta[b]benzofuran derivatives and their characterisation assisted by aligned media NMR and 13C chemical shift ab initio predictions

A new approach to the synthesis of cyclopenta[b]benzofuran derivatives via reaction of 1,3-dicarbonyl compounds with α,β,γ,δ-unsaturated aldehydes is described. The constitution and configuration of the new products have been firmly established by means of residual dipolar couplings (RDCs) and ab initio (13)C NMR chemical shift predictions.