Measurements of niobium absorption spectra in plasmas with nearly full M-shell configurations

A systematic study has been carried out on the changes in the L-shell absorption structure of niobium as a result of changing the population of the n = 3 shell from full to having vacancies in the 3d level. The niobium spectra were measured in the 2–3 keV frequency range, which spanned the 2p-nd transitions where 3 ≤ n ≤ 11. In addition to the detailed structure in these arrays the data also show 2s-4p and 2p-4s transitions and the bound-free L edge. The frequencies and widths of transition arrays, transmission between arrays, and the absorption due to the bound-free edge, can be seen in the data. The sample conditions were found from a combination of two-dimensional radiation-hydrodynamics calculations using the AWE NYM code and flux measurements using X-ray diodes, measurements of 1s-2p absorption spectra in aluminium and mixed aluminium/niobium samples. The electron temperature error, inferred from the modelling, is ±2 eV, with a density error of 30%. The data were recorded over the temperature range from 28 to 45 eV and show marked changes in the spectra over this range.The data were compared to spectra predicted by the AWE CASSANDRA [B.J.B. Crowley, J.W.O. Harris, J. Quant. Spectrosc. Radiat. Transfer 71 (2000) p. 257] opacity code. The calculated spectra were able to reproduce the measurements reasonably well. However, there are some differences in line positions that cannot be accounted for by gradients and there are differences in the array structure in the prediction and the measurements, with additional structure predicted but not seen in the measurements. There is also lower transmission on the blue side of the 2p-3d transition arrays compared to prediction.     

The axisymmetric viscoelastic contact problem with rotational friction

The boundary value problem that arises when a mechanically rough rigid punch of arbitrary axisymmetric profile is pressed against the surface of a linear aging viscoelastic half space and is also made to rotate about its axis, so that there is total slip between the contacting surfaces is analysed and solved. The moment required to make the punch rotate, on the assumption that the coefficient of friction obeys a power law or is a constant, and the total normal pressure acting on the punch may each be evaluated in terms of the history of the radius of the contact area. Application is made to the special cases where the punch has the form of (i) a cone, (ii) a paraboloid of revolution and (iii) a flat ended cylinder. Apart from case (iii) where the contract area is constant we can only find an explicit expression for the moment in terms of total pressure so long as the contact area is increasing. The case of constant total pressure and Maxwell viscoelastic material is examined in more detail.     

Nonreacting chemical transport in two-phase reservoirs — Factoring diffusive and wave properties

The vertical transport of mass, energy andn unreacting chemical species in a two-phase reservoir is analysed when capillarity can be ignored. This results in a singular system of equations, comprising mixed parabolic and hyperbolic equations. We derive a natural factorisation of these equations into diffusive and wave equations. If diffusive or conductive effects are important for onlyN–1 of the chemical species, then there areN parabolic equations, andn+2–N wave equations. Each wave equation allows for the corresponding variable to be discontinous, or equivalently, for shock propagation to occur. Steady flows were shown to allow for more than two (vapour and liquid dominated) saturations for a given mass, energy and chemical flux, but when thermal conduction and chemical diffusion are unimportant, only the vapour and liquid dominated cases appear likely to occur. For infinitesimal shocks there is a continuous flux vector for each diffusive variable. The existence of these continuous flux vectors results in significant simplifications of the corresponding wave equations. It remains an open question if continuous flux vectors exist for finite shocks. General expressions are obtained for the diffusion and wave matrices, which require no knowledge of continuous flux vectors.     

Fabricating protein immunoassay arrays on nitrocellulose using dip-pen lithography techniques

Advancements in lithography methods for printing biomolecules on surfaces are proving to be potentially beneficial for disease screening and biological research. Dip-pen nanolithography (DPN) is a versatile micro and nanofabrication technique that has the ability to produce functional biomolecule arrays. The greatest advantage, with respect to the printing mechanism, is that DPN adheres to the sensitive mild conditions required for biomolecules such as proteins. We have developed an optimised, high-throughput printing technique for fabricating protein arrays using DPN. This study highlights the fabrication of a prostate specific antigen (PSA) immunoassay detectable by fluorescence. Spot sizes are typically no larger than 8 μm in diameter and limits of detection for PSA are comparable with a commercially available ELISA kit. Furthermore, atomic force microscopy (AFM) analysis of the array surface gives great insight into how the nitrocellulose substrate functions to retain protein integrity. This is the first report of protein arrays being printed on nitrocellulose using the DPN technique and the smallest feature size yet to be achieved on this type of surface. This method offers a significant advance in the ability to produce dense protein arrays on nitrocellulose which are suitable for disease screening using standard fluorescence detection.     

Ion/molecule reactions for detecting ammonia using miniature cylindrical ion trap mass spectrometers

Gaseous ammonia, a common toxic industrial compound, is not detected readily in ion trap mass spectrometers because its molecular ion falls below the low-mass cutoff (~m/z 40) normally used when examining organic compounds. Instead, reactions of ammonia with halobenzene radical cations were used with internal electron ionization in two cylindrical ion trap miniature mass spectrometers to create a characteristic product ion by which to identify and quantify ammonia. Ammonia showed a linear response over the concentration range studied (parts per million [ppm] to parts per billion [ppb]) with limits of detection of 17 ppm and 220 ppb for experiments involving direct introduction and thermal desorption after pre-concentration, respectively. These values are comparable to ammonia's permissible exposure limit (50 ppm) and odor threshold (5 ppm). Receiver operating characteristic (ROC) curves were used to describe the method sensitivity, the probability of true positives, and the false positive rate for ammonia. A customized reaction scan function was created to select the species available for the ion/molecule reaction and set the amount of time the product ion could be accumulated in the trap. Product ion identity was verified using tandem mass spectrometry. Similar reactions with methylamine, ethylamine and the two nitriles, acetonitrile and benzonitrile, were explored.     

A novel 'fizziness' indicator

A novel colourimetric 'fizziness' indicator is described which changes colour depending on the headspace pressure of carbon dioxide above a carbonated liquid.     

Recent and potential developments in the analysis of urine: a review

Analysis of urine is a widely used diagnostic tool that traditionally measured one or, at most, a few metabolites. However, the recognition of the need for a holistic approach to metabolism led to the application of metabolomics to urine for disease diagnostics. This review looks at various aspects of urinalysis including sampling and traditional approaches before reviewing recent developments using metabolomics. Spectrometric approaches are covered briefly since there are already a number of very good reviews on NMR spectroscopy and mass spectrometry and other spectrometries are not as highly developed in their applications to metabolomics. On the other hand, there has been a recent surge in chromatographic applications dedicated to characterising the human urinary metabolome. While developments in the analysis of urine encompassing both classical approaches of urinalysis and metabolomics are covered, it must be emphasized that these approaches are not orthogonal - they both have their uses and are complementary. Regardless, the need to normalise analytical data remains an important impediment.     

Mapping the spatial overlap of excitons in a photosynthetic complex via coherent nonlinear frequency generation

We experimentally demonstrate a nonlinear spectroscopic method that is sensitive to exciton-exciton interactions in a Frenkel exciton system. Spatial overlap of one-exciton wavefunctions leads to coupling between them, resulting in two-exciton eigenstates that have the character of many single-exciton pairs. The mixed character of the two-exciton wavefunctions gives rise to a four-wave-mixing nonlinear frequency generation signal. When only part of the linear excitation spectrum of the complex is excited with three spectrally tailored pulses with separate spatial directions, a frequency-shifted third-order nonlinear signal emerges in the phase-matched direction. We employ the nonlinear response function formalism to show that the emergence of the signal is mediated by and carries information about the two-exciton eigenstates of the system. We report experimental results for nonlinear frequency generation in the Fenna-Matthews-Olson (FMO) photosynthetic pigment-protein complex. Our theoretical analysis of the signal from FMO confirms that the emergence of the frequency-shifted signal is due to the interaction of spatially overlapped excitons. In this method, the signal intensity is directly measured in the frequency domain and does not require scanning of pulse delays or signal phase retrieval. The wavefunctions of the two-exciton states contain information about the spatial overlap of excitons and can be helpful in identifying coupling strengths and relaxation pathways. We propose this method as a facile experimental means of studying exciton correlations in systems with complicated electronic structures.     

Pure optical dephasing dynamics in semiconducting single-walled carbon nanotubes

We report a detailed study of ultrafast exciton dephasing processes in semiconducting single-walled carbon nanotubes employing a sample highly enriched in a single tube species, the (6,5) tube. Systematic measurements of femtosecond pump-probe, two-pulse photon echo, and three-pulse photon echo peak shift over a broad range of excitation intensities and lattice temperature (from 4.4 to 292 K) enable us to quantify the timescales of pure optical dephasing (T(2)(*)), along with exciton-exciton and exciton-phonon scattering, environmental effects as well as spectral diffusion. While the exciton dephasing time (T(2)) increases from 205 fs at room temperature to 320 fs at 70 K, we found that further decrease of the lattice temperature leads to a shortening of the T(2) times. This complex temperature dependence was found to arise from an enhanced relaxation of exciton population at lattice temperatures below 80 K. By quantitatively accounting the contribution from the population relaxation, the corresponding pure optical dephasing times increase monotonically from 225 fs at room temperature to 508 fs at 4.4 K. We further found that below 180 K, the pure dephasing rate (1/T(2)(*)) scales linearly with temperature with a slope of 6.7 ± 0.6 μeV/K, which suggests dephasing arising from one-phonon scattering (i.e., acoustic phonons). In view of the large dynamic disorder of the surrounding environment, the origin of the long room temperature pure dephasing time is proposed to result from reduced strength of exciton-phonon coupling by motional narrowing over nuclear fluctuations. This consideration further suggests the occurrence of remarkable initial exciton delocalization and makes nanotubes ideal to study many-body effects in spatially confined systems.