Fasting status as a consideration for human serum collection and preparation prior to depletion and analysis

The use of comparative serum proteomic analysis has the potential to reveal protein expression changes present at different stages of disease progression. Depletion strategies allow for the enrichment of low-abundance proteins, which are more likely to be clinically significant biomarkers. We have observed that patient serum samples filtered through 0.22 microm cellulose acetate spin filters prior to depletion showed a variable level of retention of patient material on the upper part of the filter. This could potentially be related to the fasting status of the patient as a reduction in the lipid content of samples through the incorporation of a centrifugation step prior to filtration was found to reduce this effect. In order to determine if proteins were being selectively retained during filtration, a 2-D difference gel electrophoresis (2-D DIGE) experiment was performed. This demonstrated no significant selective retention of protein within crude serum samples. However, as this analysis was carried out on crude serum, it must be emphasised that protein loss could be manifest in the low-abundance proteins which would be masked in our analysis. Depletion of the retentate was not possible due to technical limitations, however based on our results a centrifugation step might act as an alternative to filtration in serum processing prior to depletion.     

Wideband ipsilateral measurements of middle-ear muscle reflex thresholds in children and adults

The goals of the current study were to: 1) evaluate the feasibility of a new wideband approach to measuring middle-ear muscle reflex (MEMR) status, and 2) to test the hypothesis that ipsilateral thresholds elicited with 1 or 2 kHz tones and broadband noise activators on a wideband acoustic transfer function (WATF) system are lower than thresholds elicited on a clinical system. Clinical MEMR tests have limitations, including the need for high activator levels to elicit a shift in a narrowband probe (e.g., a 0.226 or 1 kHz tone). Wideband MEMR tests using WATFs may elicit the reflex at lower levels because a wideband probe (click) is used and the threshold detection criterion can be wideband. Mean wideband MEMR thresholds across 40 normal-hearing adult ears were 2.2-4.0 dB lower than clinical MEMR thresholds, depending on the activator and specific WATF test used (admittance magnitude or energy reflectance). Wideband MEMR has potential clinical utility beyond the adult population, including use in newborn and preschool hearing screenings. In a newborn hearing screening, for example, wideband MEMR could be completed with the same system as otoacoustic emissions. However, further investigations in infants and young children are needed.     

Unexpected Self‐Sorting Self‐Assembly Formation of a [4:4] Sulfate:Ligand Cage from a Preorganized Tripodal Urea Ligand

The design and synthesis of tripodal ligands 1 – 3 based upon the N‐methyl‐1,3,5‐benzenetricarboxamide platform appended with three aryl urea arms is reported. This ligand platform gives rise to highly preorganized structures and is ideally suited for binding SO₄^2? and H₂PO₄^? ions through multiple hydrogen‐bonding interactions. The solid‐state crystal structures of 1 – 3 with SO₄^2? show the encapsulation of a single anion within a cage structure, whereas the crystal structure of 1 with H₂PO₄^? showed that two anions are encapsulated. We further demonstrate that ligand 4 , based on the same platform but consisting of two bis‐urea moieties and a single ammonium moiety, also recognizes SO₄^2? to form a self‐assembled capsule with [4:4] SO₄^2?: 4 stoichiometry in which the anions are clustered within a cavity formed by the four ligands. This is the first example of a self‐sorting self‐assembled capsule where four tetrahedrally arranged SO₄^2? ions are embedded within a hydrophobic cavity.     

Machine‐Assisted Organic Synthesis

In this Review we describe how the advent of machines is impacting on organic synthesis programs, with particular emphasis on the practical issues associated with the design of chemical reactors. In the rapidly changing, multivariant environment of the research laboratory, equipment needs to be modular to accommodate high and low temperatures and pressures, enzymes, multiphase systems, slurries, gases, and organometallic compounds. Additional technologies have been developed to facilitate more specialized reaction techniques such as electrochemical and photochemical methods. All of these areas create both opportunities and challenges during adoption as enabling technologies.     

Probing the influence of steric bulk on anion binding by triarylboranes: comparative studies of FcB(o-Tol)2, FcB(o-Xyl)2 and FcBMes2

Steric crowding brought about on pyramidalization at boron has been predicted computationally to be of central importance to the strength and selectivity of anion binding by triarylboranes. The role of steric factors in systems containing a ferrocenyl reporter unit has been systematically probed in the current study by comparison of the F(-)/CN(-) binding properties of FcB(o-Tol)(2) (1, o-Tol = C(6)H(4)Me-2), FcB(o-Xyl)(2) (2, o-Xyl = C(6)H(3)Me(2)-2,6) and FcBMes(2) (3, Mes = C(6)H(2)Me(3)-2,4,6)), both in solution and in the solid state. Somewhat surprisingly, the inclusion of an extra ortho-methyl aryl substituent (e.g. for 2/3vs.1) is found to have a relatively small effect on the binding affinities of these boranes (e.g. log(10)K(CN) = 5.94(0.02), 4.73(0.01), 5.56(0.02), for 1, 2 and 3 respectively). Consistent with this observation, the degree of pyramidalization at boron determined for the cyanide adducts [1·CN](-), [2·CN](-) and [3·CN](-) in the solid state is also found to be essentially invariant (∠C(aryl)-B-C(aryl) = 338, 337, 337°, respectively), as are the B-CN and mean B-C(aryl) distances. In the solid state at least, it is apparent that the adverse steric effects potentially brought about by increasing ortho substitution are mitigated by a greater degree of synchronous rotation of the aryl substituents about the B-C(aryl) bonds. Thus a mean inter-plane angle of 71° is observed for [1·CN](-) while the corresponding values for [2·CN](-) and [3·CN](-) are 78° and 79°.     

A note on the functional calculus for unbounded self-adjoint operators

Two theorems of Riesz and Lorch (1936) are used to pass directly from the functional calculus for bounded symmetric operators to that for unbounded self-adjoint operators, thereby considerably shortening the passage via the spectral resolution for unbounded self-adjoint operators, and making particularly transparent the manner in which properties of the functional calculus for bounded operators are inherited by those which are unbounded.     

Nuclear structure relevant to neutrinoless double beta decay: 76Ge and 76Se

The possibility of observing neutrinoless double beta decay offers the opportunity of determining the effective neutrino mass if the nuclear matrix element were known. Theoretical calculations are uncertain, and measurements of the occupations of valence orbits by nucleons active in the decay can be important. The occupation of valence neutron orbits in the ground states of 76Ge (a candidate for such decay) and 76Se (the daughter nucleus) were determined by precisely measuring cross sections for both neutron-adding and removing transfer reactions. Our results indicate that the Fermi surface is much more diffuse than in theoretical calculations. We find that the populations of at least three orbits change significantly between these two ground states while in the calculations, the changes are confined primarily to one orbit.     

A sensitivity analysis of the point reference global correlation (PRGC) technique for spatio-temporal correlations in turbulent flows

The point reference global correlation (PRGC) technique which combines single and global measurements as proposed by Chatellier and Fitzpatrick (Exp Fluids 38(5):563–757, 2005) is of significant interest for the analysis of the turbulent statistics for noise source modeling in jet flows as it allows the 2D spatio-temporal correlation functions to be obtained over a region of the flow. This enables the statistical characteristics including inhomogeneous and anisotropic features to be determined. The sensitivity of the technique is examined in some detail for the specific case of laser doppler velocimetry (LDV) and particle image velocimetry (PIV). Simulated data are used to enable a parametric study of the accuracy of the PRGC technique to be determined as a function of the various measurement parameters. The sample frequencies and the number of samples of both the LDV and PIV signals are shown to be critical to errors associated with the estimated spatio-temporal correlations and that low data rates can lead to significant errors in the estimates. Measurements performed in single stream and co-axial jet flows at Mach 0.24 using PIV and LDV systems are reported and the 2D space–time correlation functions for these flows are determined using the PRGC technique. The results are discussed in the context of noise source modeling for jet flows.