p-cresol as a reversible acylium ion scavenger in solid-phase peptide synthesis

In this work we have defined the nature of the p-cresol and p-thiocresol adducts generated from acylium ions during HF cleavage, following contemporary Boc/benzyl solid-phase peptide synthesis. Contrary to the results in previous reports, we found that both p-cresol and p-thiocresol predominantly form. aryl esters under typical cleavage conditions. Initially we investigated a number of small peptides containing either a single glutamate residue or a C-terminal long-chain amino acid which allowed us to unambiguously characterize the scavenged side products. Whereas, the p-cresol esters are stable at 0 degrees C they rearrange irreversibly at higher temperatures (5-20 degrees C) to form aryl ketones. By contrast, p-thiocresol esters do not undergo a Fries rearrangement but readily undergo further additions of p-thiocresol to form ketenebisthioacetals and trithio ortho esters, even at low temperatures. Importantly, we found by LC/MS and FT-ICR MS analysis that peptides containing p-cresol esters at glutamyl side chains are susceptible to amidation and fragmentation reactions at these sites during standard mild base workup procedures. The significance of these side reactions was further demonstrated in the synthesis of neutrophil immobilization factor, a 26-residue peptide, containing four glutamic acid residues. The side reactions were largely avoided by mild hydrogen peroxide-catalyzed hydrolysis which converted the p-cresol adducts to the free carboxylic acids in near quantitative yield. The choice of p-cresol as a reversible acylium ion scavenger when coupled with the simple workup conditions described is broadly applicable to Boc/benzyl peptide synthesis and will significantly enhance the quality of peptides produced.

Annealing of ion implanted gallium nitride

In this paper, we examine Si and Te ion implant damage removal in GaN as a function of implantation dose, and implantation and annealing temperature. Transmission electron microscopy shows that amorphous layers, which can result from high-dose implantation, recrystallize between 800 and 1100 °C to very defective polycrystalline material. Lower-dose implants (down to 5 × 1013 cm – 2), which are not amorphous but defective after implantation, also anneal poorly up to 1100 °C, leaving a coarse network of extended defects. Despite such disorder, a high fraction of Te is found to be substitutional in GaN both following implantation and after annealing. Furthermore, although elevated-temperature implants result in less disorder after implantation, this damage is also impossible to anneal out completely by 1100 °C. The implications of this study are that considerably higher annealing temperatures will be needed to remove damage for optimum electrical properties. ©1998 American Institute of Physics.

A comparison of bichromatic beam splitters for atoms

We analyse and compare various aspects of the performance of atomic beam splitters fur two- and three-level atoms, both of which use bichromatic optical fields. We calculate the extent to which spontaneous emission degrades the sharpness of the splitting, and how it might degrade the visibility of an idealised atom interferometer which includes either beam splitting mechanism. (C) 1998 Elsevier Science B.V.

Decoherence in ion traps due to laser intensity and phase fluctuations

We consider one source of decoherence for a single trapped ion due to intensity and phase fluctuations in the exciting laser pulses. For simplicity we assume that the stochastic processes involved are white noise processes, which enables us to give a simple master equation description of this source of decoherence. This master equation is averaged over the noise, and is sufficient to describe the results of experiments that probe the oscillations in the electronic populations as energy is exchanged between the internal and electronic motion. Our results are in good qualitative agreement with recent experiments and predict that the decoherence rate will depend on vibrational quantum number in different ways depending on which vibrational excitation sideband is used.

Measurement and state preparation via ion trap quantum computing

We investigate in detail the effects of a QND vibrational number measurement made on single ions in a recently proposed measurement scheme for the vibrational state of a register of ions in a linear rf trap [C. D'HELON and G. J. MILBURN, Phys Rev. A 54, 5141 (1996)]. The performance of a measurement shows some interesting patterns which are closely related to searching.

Morphine has a dual concentration-dependent effect on K+-evoked substance P release from rat peripheral airways

Our previous investigations of possible lung mechanisms underlying the effectiveness of nebulized morphine for the relief of dyspnoea, have shown a high density of non-conventional opioid binding sites in rat airways with similar binding characteristics (opioid alkaloid-sensitive, opioid peptide-insensitive) to that of putative mu(3)-opioid receptors on immune cells. To investigate whether these lung opioid binding sites are functional receptors, this study was designed to determine (using superfusion) whether morphine modulates the K+-evoked release of the pro-inflammatory neuropeptide, substance P (SP), from rat peripheral airways. Importantly, K+-evoked SP release was Ca2+-dependent, consistent with vesicular release. Submicromolar concentrations of morphine (1 and 200 nM) inhibited K+-evoked SP release from rat peripheral airways in a naloxone (1 mu M) reversible manner. By contrast, 1 mu M morphine enhanced K+-evoked SP release and this effect was not reversed by 1 mu M naloxone. However, 100 mu M naloxone not only antagonized the facilitatory effect of 1 mu M morphine on K+-evoked SP release from rat peripheral airways but it inhibited release to a similar extent as 200 nM morphine. It is possible that these latter effects are mediated by non-conventional opioid receptors located on mast cells, activation of which causes naloxone-reversible histamine release that in turn augments the release of SP from sensory nerve terminals in the peripheral airways. Clearly, further studies are required to investigate this possibility. (C) 1997 Academic Press Limited.

Asymptotic limits of a self-dual Ginzburg-Landau functional in bounded domains

In the author's joint paper [HJS] with Jest and Struwe, we discuss asymtotic limits of a self-dual Ginzburg-Landau functional involving a section of a line bundle over a closed Riemann surface and a connection on this bundle. In this paper, the author generalizes the above results [HJS] to the case of bounded domains.

Decoherence and fidelity in ion traps with fluctuating trap parameters

We consider two different kinds of fluctuations in an ion trap potential: external fluctuating electrical fields, which cause statistical movement (wobbling) of the ion relative to the center of the trap, and fluctuations of the spring constant, which an due to fluctuations of the ac component of the potential applied in the Paul trap for ions. We write down master equations for both cases and, averaging out the noise, obtain expressions for the heating of the ion. We compare our results to previous results for far-off resonance optical traps and heating in ion traps. The effect of fluctuating external electrical fields for a quantum gate operation (controlled-NOT) is determined and the fidelity for that operation derived. [S1050-2947(99)06005-9].

Sensitivity of multiple frequency bioelectrical impedance analysis to changes in ion status

Bioelectrical impedance analysis has found extensive application as a simple noninvasive method for the assessment of body fluid volumes, The measured impedance is, however, not only related to the volume of fluid but also to its inherent resistivity. The primary determinant of the resistivities of body fluids is the concentration of ions. The aim of this study was to investigate the sensitivity of bioelectrical impedance analysis to bodily ion status. Whole body impedance over a range of frequencies (4-1012 kHz) of rats was measured during infusion of various concentrations of saline into rats concomitant with measurement of total body and intracellular water by tracer dilution techniques. Extracellular resistance (R-o), intracellular resistance (R-i) and impedance at the characteristic frequency (Z(c)) were calculated. R-o and Z(c) were used to predict extracellular and total body water respectively using previously published formulae. The results showed that whilst R-o and Z(c) decreased proportionately to the amount of NaCl infused, R-i increased only slightly. Impedances at the end of infusion predicted increases iu TBW and ECW of approximately 4-6% despite a volume increase of less than 0.5% in TBW due to the volume of fluid infused. These data are discussed in relation to the assumption of constant resistivity in the prediction of fluid volumes from impedance data.

Assessment of limb muscle and adipose tissue by dual-energy X-ray absorptiometry using magnetic resonance imaging for comparison

OBJECTIVE: To use magnetic resonance imaging (MRI) to validate estimates of muscle and adipose tissue (AT) in lower limb sections obtained by dual-energy X-ray absorptiometry (DXA) modelling. DESIGN: MRI measurements were used as reference for validating limb muscle and AT estimates obtained by DXA models that assume fat-free soft tissue (FFST) comprised mainly muscle: model A accounted for bone hydration only; model B also applied constants for FFST in bone and skin and fat in muscle and AT; model C was as model B but allowing for variable fat in muscle and AT. SUBJECTS: Healthy men (n = 8) and women (n = 8), ages 41 - 62 y; mean (s.d.) body mass indices (BMIs) of 28.6 (5.4) kg/m(2) and 25.1 (5.4) kg/m2, respectively. MEASUREMENTS: MRI scans of the legs and whole body DXA scans were analysed for muscle and AT content of thigh (20 cm) and lower leg (10 cm) sections; 24 h creatinine excretion was measured. RESULTS: Model A overestimated thigh muscle volume (MRI mean, 2.3 l) substantially (bias 0.36 l), whereas model B underestimated it by only 2% (bias 0.045 l). Lower leg muscle (MRI mean, 0.6 l) was better predicted using model A (bias 0.04 l, 7% overestimate) than model B (bias 0.1 l, 17% underestimate). The 95% limits of agreement were high for these models (thigh,+/- 20%; lower leg,+/- 47%). Model C predictions were more discrepant than those of model B. There was generally less agreement between MRI and all DXA models for AT. Measurement variability was generally less for DXA measurements of FFST (coefficient of variation 0.7 - 1.8%) and fat (0.8 - 3.3%) than model B estimates of muscle (0.5-2.6%) and AT (3.3 - 6.8%), respectively. Despite strong relationships between them, muscle mass was overestimated by creatinine excretion with highly variable predictability. CONCLUSION: This study has shown the value of DXA models for assessment of muscle and AT in leg sections, but suggests the need to re-evaluate some of the assumptions upon which they are based.

Quantum and classical chaos for a single trapped ion

In this paper we investigate the quantum and classical dynamics of a single trapped ion subject to nonlinear kicks derived from a periodic sequence of Gaussian laser pulses. We show that the classical system exhibits: diffusive growth in the energy, or heating,'' while quantum mechanics suppresses this heating. This system may be realized in current single trapped-ion experiments with the addition of near-field optics to introduce tightly focused laser pulses into the trap.

'Tetol': a stereo-rigid four-strand motif for alkali and alkaline earth metal ion coordination

The tetraalcohol 2,3,5,6-endo,endo,endo,endo-tetrakis(hydroxymethyl]bicyclo[2.2.1]heptane (tetol, 1) has been prepared and crystallises readily as the lithium(I) complex [Li(1)(2)]Cl, forming an oligomeric multi-chain structure in which pairs of alcohols from two crystallographically independent tetol molecules bind lithium ions tetrahedrally. However, formation of monomeric structures in solution is inferred from electrospray mass spectroscopy, which has also shown evidence of exchange of lithium ion in the complexed species by added alkaline earth ions. (C) 2000 Elsevier Science S.A. All rights reserved.

Entangled coherent-state qubits in an ion trap

We show how entangled qubits can be encoded as entangled coherent states of two-dimensional center-of-mass vibrational motion for two ions in an ion trap. The entangled qubit state is equivalent to the canonical Bell state, and we introduce a proposal for entanglement transfer from the two vibrational modes to the electronic states of the two ions in order for the Bell state to be detected by resonance fluorescence shelving methods.

Dual processes in recognition: Does a focus on measurement operations provide a sufficient foundation?

Current theoretical thinking about dual processes in recognition relies heavily on the measurement operations embodied within the process dissociation procedure. We critically evaluate the ability of this procedure to support this theoretical enterprise. We show that there are alternative processes that would produce a rough invariance in familiarity (a key prediction of the dual-processing approach) and that the process dissociation procedure does not have the power to differentiate between these alternative possibilities. We also show that attempts to relate parameters estimated by the process dissociation procedure to subjective reports (remember-know judgments) cannot differentiate between alternative dual-processing models and that there are problems with some of the historical evidence and with obtaining converging evidence. Our conclusion is that more specific theories incorporating ideas about representation and process are required.

A dual catalyst bed system for the elimination of hydrogen from CO2 feed gas in urea synthesis

A dual catalyst bed system (Au/Fe2O3 + Pt-Pd/Al2O3) for eliminating hydrogen from the CO2 feed gas in urea synthesis is found to be far superior to commercially available and patented catalysts in catalytic activity. At relatively low temperatures, hydrogen is eliminated and coexistent CO is also oxidized completely to useful CO2. This can avoid effectively the accidental explosion of hydrogen-oxygen-ammonia mixed gases, thus ensuring the safety of urea synthesis.