Composition profiling of seized ecstasy tablets by Raman spectroscopy

Raman spectroscopy with far-red excitation has been investigated as a simple and rapid technique for composition profiling of seized ecstasy (MDMA, N-methyl-3,4-methylenedioxyamphetamine) tablets. The spectra obtained are rich in vibrational bands and allow the active drug and excipient used to bulk the tablets to be identified. Relative band heights can be used to determine drug/excipient ratios and the degree of hydration of the drug while the fact that 50 tablets per hour can be analysed allows large numbers of spectra to be recorded. The ability of Raman spectroscopy to distinguish between ecstasy tablets on the basis of their chemical composition is illustrated here by a sample set of 400 tablets taken from a large seizure of > 50000 tablets that were found in eight large bags. The tablets are all similar in appearance and carry the same logo. Conventional analysis by GC-MS showed they contained MDMA. Initial Raman studies of samples from each of the eight bags showed that despite some tablet-to-tablet variation within each bag the contents could be classified on the basis of the excipients used. The tablets in five of the bags were sorbitol-based, two were cellulose-based and one bag contained tablets with a glucose excipient. More extensive analysis of 50 tablets from each of a representative series of sample bags gave distribution profiles that showed the contents of each bag were approximately normally distributed about a mean value, rather than being mixtures of several discrete types. Two of the sorbitol-containing sample sets were indistinguishable while a third was similar but not identical to these, in that it contained the same excipient and MDMA with the same degree of hydration but had a slightly different MDMA/sorbitol ratio. The cellulose-based samples were badly manufactured and showed considerable tablet-to-tablet variation in their drug/excipient ratio while the glucose-based tablets had a tight distribution in their drug/excipient ratios. The degree of hydration in the MDMA feedstocks used to manufacture the cellulose-, glucose- and sorbitol-based tablets were all different from each other. This study, because it centres on a single seizure of physically similar tablets with the same active drug, highlights the fact that simple physical descriptions coupled with active drug content do not in themselves fully characterize the nature of the seized materials. There is considerable variation in the composition of the tablets within this single seizure and the fact that this variation can be detected from Raman spectra demonstrates that the potential benefits of obtaining highly detailed spectra can indeed translate into information that is not readily available from other methods but would be useful for tracing of drug distribution networks.

Stellar rotation in the Hyades and Praesepe: gyrochronology and braking time-scale

We present the results of photometric surveys for stellar rotation in the Hyades and in Praesepe, using data obtained as part of the SuperWASP exoplanetary transit-search programme. We determined accurate rotation periods for more than 120 sources whose cluster membership was confirmed by common proper motion and colour-magnitude fits to the clusters' isochrones. This allowed us to determine the effect of magnetic braking on a wide range of spectral types for expected ages of ˜600 Myr for the Hyades and Praesepe. Both clusters show a tight and nearly linear relation between J-Ks colour and rotation period in the F, G and K spectral range. This confirms that loss of angular momentum was significant enough that stars with strongly different initial rotation rates have converged to the same rotation period for a given mass, by the ages of Hyades and Praesepe. In the case of the Hyades, our colour-period sequence extends well into the M dwarf regime and shows a steep increase in the scatter of the colour-period relation, with identification of numerous rapid rotators from ˜0.5 Msun down to the lowest masses probed by our survey (˜0.25 Msun). This provides crucial constraints on the rotational braking time-scales and further clears the way to use gyrochronology as an accurate age measurement tool for main-sequence stars.

Enhanced proton flux in the MeV range by defocused laser irradiation

Thin Al foils (50 nm and 6 mu m) were irradiated at intensities of up to 2x10(19) W cm(-2) using high contrast (10(8)) laser pulses. Ion emission from the rear of the targets was measured using a scintillator-based Thomson parabola and beam sampling 'footprint' monitor. The variation of the ion spectra and beam profile with focal spot size was systematically studied. The results show that while the maximum proton energy is achieved around tight focus for both target thicknesses, as the spot size increases the ion flux at lower energies is seen to peak at significantly increased spot sizes. Measurements of the proton footprint, however, show that the off-axis proton flux is highest at tight focus, indicating that a previously identified proton deflection mechanism may alter the on-axis spectrum. One-dimensional particle-in-cell modelling of the experiment supports our hypothesis that the observed change in spectra with focal spot size is due to the competition of two effects: decrease in laser intensity and an increase in proton emission area.

Third harmonic order imaging as a focal spot diagnostic for high intensity laser-solid interactions

As the state of the art for high power laser systems increases from terawatt to petawatt level and beyond, a crucial parameter for routinely monitoring high intensity performance is laser spot size on a solid target during an intense interaction in the tight focus regime ( 10(19) Wcm(-2) is demonstrated experimentally and shown to provide the basis for an effective focus diagnostic. Importantly, this technique is also shown to allow in-situ diagnosis of focal spot quality achieved after reflection from a double plasma mirror setup for very intense high contrast interactions (> 10(20) Wcm(-2)) an important application for the field of high laser contrast interaction science.

An expression vector containing a rhamnose-inducible promoter provides tightly regulated gene expression in Burkholderia cenocepacia

Infection of the respiratory tract caused by Burkholderia cepacia complex poses a serious risk for cystic fibrosis (CF) patients due to the high morbidity and mortality associated with the chronic infection and the lack of efficacious antimicrobial treatments. A detailed understanding of the pathogenicity of B. cepacia complex infections is hampered in part by the limited availability of genetic tools and the inherent resistance of these isolates to the most common antibiotics used for genetic selection. In this study, we report the construction of an expression vector which uses the rhamnose-regulated P(rhaB) promoter of Escherichia coli. The functionality of the vector was assessed by expressing the enhanced green fluorescent protein (eGFP) gene (e-gfp) and determining the levels of fluorescence emission. These experiments demonstrated that P(rhaB) is responsive to low concentrations of rhamnose and it can be effectively repressed with 0.2% glucose. We also demonstrate that the tight regulation of gene expression by P(rhaB) promoter allows us to extend the capabilities of this vector to the identification of essential genes.

The M17 leucine aminopeptidase of the malaria parasite Plasmodium falciparum:importance of active site metal ions in the binding of substrates and inhibitors

The M17 leucine aminopeptidase of the intraerythrocytic stages of the malaria parasite Plasmodium falciparum (PfLAP) plays a role in releasing amino acids from host hemoglobin that are used for parasite protein synthesis, growth, and development. This enzyme represents a target at which new antimalarials could be designed since metalloaminopeptidase inhibitors prevent the growth of the parasites in vitro and in vivo. A study on the metal ion binding characteristics of recombinant P. falciparum M17 leucine aminopeptidase (rPfLAP) shows that the active site of this exopeptidase contains two metal-binding sites, a readily exchangeable site (site 1) and a tight binding site (site 2). The enzyme retains activity when the metal ion is removed from site 1, while removal of metal ions from both sites results in an inactive apoenzyme that cannot be reactivated by the addition of divalent metal cations. The metal ion at site 1 is readily exchangeable with several divalent metal ions and displays a preference in the order of preference Zn(2+) > Mn(2+) > Co(2+) > Mg(2+). While it is likely that native PfLAP contains a Zn(2+) in site 2, the metal ion located in site 1 may be dependent on the type and concentration of metal ions in the cytosolic compartment of the parasite. Importantly, the type of metal ion present at site 1 influences not only the catalytic efficiency of the enzyme for peptide substrates but also the mode of binding by bestatin, a metal-chelating inhibitor of M17 aminopeptidases with antimalarial activity.

Fast electron penetration in laser-irradiated solids

In this letter we present data comparing the yield of Cu K-alpha radiation for foils of differing thickness irradiated with a Ti:Sapphire laser generating 40 fs pulses at 800 nm and incident at 45 degrees. At tight focus, the yields for all thicknesses are similar, whilst away from best focus there are clear differences. We discuss the origin of these similarities and differences in terms of the penetration of fast electrons into the foil and the possible importance of refluxing of fast electrons as they reach the non-irradiated side of the foil.

Greatly enhanced arsenic shoot assimilation in rice leads to elevated grain levels compared to wheat and barley

Paired grain, shoot, and soil of 173 individual sample sets of commercially farmed temperate rice, wheat, and barley were surveyed to investigate variation in the assimilation and translocation of arsenic (As). Rice samples were obtained from the Carmargue (France), Doñana (Spain), Cadiz (Spain), California, and Arkansas. Wheat and barleywere collected from Cornwall and Devon (England) and the east coast of Scotland. Transfer of As from soil to grain was an order of magnitude greater in rice than for wheat and barley, despite lower rates of shoot-to-grain transfer. Rice grain As levels over 0.60 microg g(-1) d. wt were found in rice grown in paddy soil of around only 10 microg g(-1) As, showing that As in paddy soils is problematic with respect to grain As levels. This is due to the high shoot/soil ratio of approximately 0.8 for rice compared to 0.2 and 0.1 for barley and wheat, respectively. The differences in these transfer ratios are probably due to differences in As speciation and dynamics in anaerobic rice soils compared to aerobic soils for barley and wheat. In rice, the export of As from the shoot to the grain appears to be under tight physiological control as the grain/shoot ratio decreases by more than an order of magnitude (from approximately 0.3 to 0.003 mg/kg) and as As levels in the shoots increase from 1 to 20 mg/kg. A down regulation of shoot-to-grain export may occur in wheat and barley, but it was not detected at the shoot As levels found in this survey. Some agricultural soils in southwestern England had levels in excess of 200 microg g(-1) d. wt, although the grain levels for wheat and barley never breached 0.55 microg g(-1) d. wt. These grain levels were achieved in rice in soils with an order of magnitude lower As. Thus the risk posed by As in the human food-chain needs to be considered in the context of anaerobic verses aerobic ecosystems.

The electronic band structure of indium selenide:Photoemission and theory

The electronic band structure of vacuum cleaved single-crystal indium selenide has been investigated by X-ray and ultraviolet photoelectron spectroscopy. The valence band consists of three well separated groups, one derived from the Se 4s levels, and two derived from p-like wavefunctions. The band structure and valence band density of states has been calculated using a tight-binding single-layer approximation and all the major features in the experimental spectra are well accounted for. The spin-orbit splitting and electron loss structure associated with the In 4d core level is also reported.

Theoretical and photoemission studies of the band structure of CdI

The band structure of CdI has been calculated using a modified semi-empirical tight-binding method and the results obtained have been compared with both angularly averaged and angularly resolved photoemission spectra. The theoretically computed density of states distribution is in excellent agreement with angularly averaged results and all the main features observed experimentally are reproduced in the theory. Angularly resolved spectra have been used to draw up energy band dispersion curves directly and agreement with calculated bands in both the Gamma M and Gamma K directions of the Brillouin zone is good.

A theoretical study of the effects of lithium intercalation on the electronic structure of TiS

The band structure of the intercalation complex of LiTiS has been computed using a semi-empirical tight-binding method and this is compared with the results of a revised TiS calculation. The results obtained confirm that changes in the basic electrical characteristics of TiS, which occur when it is intercalated with lithium, can be attributed to a rigid-band filling of its lowest unoccupied electron states as has previously been proposed. However, they also suggest that intercalation can act to alter the nature and the dispersion of some of the energy bands in the unintercalated crystal. The bands which are most affected by the process are those which derive from orbitals which have the same symmetry as the lithium 2s orbital, namely, the titanium 4s conduction level and the tightly bound sulphur 3s levels.

The band structures of gallium and indium selenide

The band structures of the group III-VI monochalcogenides GaSe and InSe have been calculated using a semi-empirical tight-binding method in a two-dimensional approximation. Many of the discrepancies between experimental work and previous calculations for GaSe have been resolved. The results for InSe appear for the first time.

Macroscopic limit of time-dependent density-functional theory for adiabatic local approximations of the exchange-correlation kernel

Time-dependent density-functional theory is a rather accurate and efficient way to compute electronic excitations for finite systems. However, in the macroscopic limit (systems of increasing size), for the usual adiabatic random-phase, local-density, or generalized-gradient approximations, one recovers the Kohn-Sham independent-particle picture, and thus the incorrect band gap. To clarify this trend, we investigate the macroscopic limit of the exchange-correlation kernel in such approximations by means of an algebraical analysis complemented with numerical studies of a one-dimensional tight-binding model. We link the failure to shift the Kohn-Sham spectrum of these approximate kernels to the fact that the corresponding operators in the transition space act only on a finite subspace.

Programmable motion and separation of single magnetic particles on patterned magnetic surfaces

Motion of single micrometer-sized magnetic particles on patterned magnetic surfaces is controlled by a rotating magnetic field (see Figure and cover). Patterns of thin-film magnetic elements are tailored to form transport lines. Individual particles are separated by adding junctions to the transport lines. The method can improve existing applications in biotechnology and generate new ones in life sciences.

Dressing Plasmons in Particle-in-Cavity Architectures

Placing metallic nanoparticles inside cavities, rather than in dimers, greatly improves their plasmonic response. Such particle-in-cavity (PIC) hybrid architectures are shown to produce extremely strong field enhancement at the particle cavity junctions, arising from the cascaded focusing of large optical cross sections into small gaps. These simply constructed PIC structures produce the strongest field enhancement for coupled nanoparticles, up to 90% stronger than for a dimer. The coupling is found to follow a universal power law with particle surface separation, both for field enhancements and resonant wavelength shifts. Significantly enhanced Raman signals are experimentally observed for molecules adsorbed in such PIC structures, in quantitive agreement with theoretical calculations. PIC architectures may have important implications in many applications, such as reliable single molecule sensing and light harvesting in plasmonic photovoltaic devices.