Thermal Decomposition of 3'-Azidothymidine

The kinetics of thermal decomposition of 3'-azidothymidine (AZT) in melt at 140-201°C were studied by the thermogravimetric and manometric methods. The process follows the first-order kinetics and is decribed by the Arrhenius equation: k = 1014.7±0.5 exp[-(38100±900)/RT] (1/s). The kinetic and activation parameters are typical of thermal decomposition of aliphatic azides; they suggest that decomposition of the azido group is the rate-determining stage. The formation of nitrogen (1 mol per mole of AZT), furan, methyl alcohol, water, and carbon dioxide was confirmed by mass spectrometry. Thymine was found to be one of the condensed products of thermal decomposition of 3'-azidothymidine.     

A truncated Kv1.1 protein in the brain of the <Emphasis Type="Italic">megencephaly</Emphasis>mouse: expression and interaction

Background  

The megencephaly mouse, mceph/mceph, is epileptic and displays a dramatically increased brain volume and neuronal count. The responsible mutation was recently revealed to be an eleven base pair deletion, leading to a frame shift, in the gene encoding the potassium channel Kv1.1. The predicted MCEPH protein is truncated at amino acid 230 out of 495. Truncated proteins are usually not expressed since nonsense mRNAs are most often degraded. However, high Kv1.1 mRNA levels in mceph/mceph brain indicated that it escaped this control mechanism. Therefore, we hypothesized that the truncated Kv1.1 would be expressed and dysregulate other Kv1 subunits in the mceph/mceph mice.     

The NMDA antagonist memantine affects training induced motor cortex plasticity – a study using transcranial magnetic stimulation [ISRCTN65784760]

Background  

Training of a repetitive synchronised movement of two limb muscles leads to short-term plastic changes in the primary motor cortex, which can be assessed by transcranial magnetic stimulation (TMS) mapping. We used this paradigm to study the effect of memantine, a NDMA antagonist, on short-term motor cortex plasticity in 20 healthy human subjects, and we were especially interested in possible differential effects of different treatment regimens. In a randomised double-blinded cross over study design we therefore administered placebo or memantine either as a single dosage or as an ascending dosage over 8 days. Before and after one hour of motor training, which consisted of a repetitive co-contraction of the abductor pollicis brevis (APB) and the deltoid muscle, we assessed the motor output map of the APB muscle by TMS under the different conditions.     

Selective polarization inversion of protons in rotating solids

The selective inversion of lines under phase modulated Lee-Goldburg (PMLG) decoupling in MAS proton spectroscopy is demonstrated. Short pulses inserted between consecutive PMLG irradiation intervals selectively invert the polarization of an on-resonance line while sustaining a high resolution proton evolution. The pulse scheme is combined with windowed-PMLG detection to obtain a one-dimensional high resolution spectrum with one of the proton lines inverted. Initial preparation of the protons in selectively inverted states can be used to follow the flow of polarization during spin diffusion. Examples of proton-proton spin exchange in alanine and histidine are demonstrated. Selective inversion is also used in conjunction with proton carbon LG-cross-polarization to achieve carbon spectra with lines characterized by different polarization states.     

Platinum stilbazoles: ring-walking coupled with aryl-halide bond activation

The reaction between tetrakis(triethylphosphine)platinum(0) and 4-[trans-2-(4-bromophenyl)vinyl]pyridine (1) is examined. Initially, the metal center coordinates to the bridging double bond of 1. Complexes 2 and 3 were fully characterized, and their X-ray crystallography structures are presented. Upon heating, either in solution or in the solid state, complex 2 undergoes C-Br oxidative addition to give complex 3. Kinetic studies revealed that this conversion is unimolecular and does not involve dissociation of the metal center from the double bond. Density functional studies show that a plausible mechanism involves the metal center "walking" around the pi-system from the bridging C=C double bond to the C-Br bond.     

On-line electrochemically controlled solid-phase extraction interfaced to electrospray and inductively coupled plasma mass spectrometry

Electrochemically controlled solid-phase extractions of anions were interfaced on-line to electrospray mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS), using polypyrrole coated electrodes and a thin-layer electrochemical (EC) flow cell. The results indicate that electrochemically controlled solid-phase extraction (EC-SPE) can be used as a versatile potential controlled sample preparation technique for a range of anions and that the properties of the polypyrrole coatings can be modified by altering the electrodeposition conditions. In the present study, the influence of interfering anions (i.e., fluoride and sulfate), and the anion used during the electropolymerisation, on the bromide extraction recovery was investigated for EC-SPE interfaced to ICP-MS. The results of these experiments show that the interference due to the presence of similar concentrations of sulfate can be reduced when using a polypyrrole coating electropolymerised in the presence of bromide ions. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements were also used to study the morphology of the coatings, as well as the variations in the film thickness within the coatings. The effect of different desorption techniques on the bromide preconcentration factor in the ICP-MS on-line flow system was also examined. Stopped-flow desorption was found to give rise to significantly increased preconcentration factors in comparison with desorptions in flowing solutions. While the desorption efficiency depends on the type of desorption electrolyte (the electrolyte in which the desorption takes place), due to the competing influx of cations, the influence of the pH on the switching charge of the polypyrrole coating was found to be small, at constant ionic strength. To study the applicability of the EC-SPE technique with respect to real samples, investigations were also made with tap water samples spiked with different bromide concentrations. The results of these experiments, which were carried out using a modified thin-layer EC flow cell allowing in situ polymerisation of polypyrrole yielding a polymer plug covering the cross section of the channel, demonstrate that 3 microM concentrations of bromide could be detected in the tap water sample. This demonstrates that the extraction technique allows extractions of low concentrations of ions in the presence of significantly higher concentrations of other similar ions. The fact that the extraction and desorption steps are electrochemically controlled makes EC-SPE particularly well suited for inclusion in miniaturised lab-on-a-chip systems.     

Generalized ellipsometric method for the determination of all the optical constants of the system: Optically absorbing film on an absorbing substrate

A numerical method has been developed to evaluate all the optical parameters of the system of an optically absorbing film on an absorbing substrate using ellipsometric measurements. The generality and validity of the algorithm has been investigated for different ideal cases. In addition the effects of the actual limited precision of ellipsometric measurements as well as the problem of multiple solutions have been studied.     

Signal enhancement in 5QMAS spectra of spin-5/2 quadrupolar nuclei

5QMAS experiments on spin-5/2 systems display a low sensitivity compared with their 3QMAS counterparts. Nevertheless, the superior resolution of 5QMAS over 3QMAS makes these experiments a favorable choice for many materials. We report an enhancement scheme for the 5QMAS experiment, using an improved five-quantum excitation pulse scheme combined with a FAM-II conversion pulse. The results are verified experimentally on a polycrystalline sample of gamma-(27)Al(2)O(3), showing an enhancement factor of 2.4 over the simple two-pulse (CW) 5QMAS scheme. Numerical computations of the efficiency parameter epsilon support these results.     

Investigation of transverse galloping in the presence of structural nonlinearities: theory and experiment

Nonlinear Dynamics - We formulate and experimentally validate a theoretical reduced-order model for the transverse galloping of nonlinear structures, namely a pair of identical, parallel-oriented...