T-odd momentum correlation in radiative β decay

The triple-product correlations observable in ordinary neutron or nuclear beta decay are all naively T violating and can connect, through an assumption of CPT invariance, to constraints on sources of CP violation beyond the Standard Model. They are also spin dependent. In this context the study of radiative beta decay opens a new possibility, in that a triple-product correlation can be constructed from momenta alone. Consequently its measurement would constrain new spin-independent sources of CP violation. We will describe these in light of the size of the triple momentum correlation in the decay rate arising from electromagnetic final-state interactions in the Standard Model. Our expression for the corresponding T-odd asymmetry is exact in ${\cal O}(\alpha)$ up to terms of recoil order, and we evaluate it numerically under various kinematic conditions. We consider the pattern of the asymmetries in nuclear β decays and show that the asymmetry can be suppressed in particular cases, facilitating searches for new sources of CP violation in such processes.     

Structural and Functional Consequences of the Weak Binding of Chlorin e6 to Bovine Rhodopsin

The chlorophyll‐derivative chlorin e6 (Ce6) identified in the retinas of deep‐sea ocean fish is proposed to play a functional role in red bioluminescence detection. Fluorescence and ¹H NMR spectroscopy studies with the bovine dim‐light photoreceptor, rhodopsin, indicate that Ce6 weakly binds to it with μm affinity. Absorbance spectra prove that red light sensitivity enhancement is not brought about by a shift in the absorbance maximum of rhodopsin. ¹⁹F NMR experiments with samples where ¹⁹F labels are either placed at the cytoplasmic binding site or incorporated as fluorinated retinal indicate that the cytoplasmic domain is highly perturbed by binding, while little to no changes are detected near the retinal. Binding of Ce6 also inhibits G‐protein activation. Chemical shift changes in ¹H‐¹⁵N NMR spectroscopy of ¹⁵N‐Trp labeled bovine rhodopsin reveal that Ce6 binding perturbs the entire structure. These results provide experimental evidence that Ce6 is an allosteric modulator of rhodopsin.     

Luminescence characteristics of InAlP---InGaP heterostructures having native-oxide windows

Data are presented on the luminescence characteristics of InGaP/InAlP heterostructures with oxidized InAlP cladding layers grown by metalorganic chemical vapor deposition. The structures are grown on GaAs substrates and consist of either a 20 nm thick In_0.5Ga_0.5P quantum well or a 0.75 μm InGaP layer sandwiched between two InAlP bulk barriers or between two 10-period In_0.5Al_0.5P/In_xGa_1−xP strain-modulated superlattice heterobarriers, where x varies from 0.5 to 0.45 and the period of the superlattice is 3 nm. The top InAlP cladding layer of the InAlP/InGaP heterostructures is oxidized for 2–5.5 h at 500°C in an ambient of H₂O vapor saturated in a N₂ carrier gas. Photoluminescence and time-resolved photoluminescence studies at room temperature show that, as a result of the oxidation of a portion of the top InAlP cladding layer, the photoluminescence emission intensity and lifetime from the InGaP QWs increase significantly.     

Discrete tomography: Determination of finite sets by X-rays

We study the determination of finite subsets of the integer lattice , , by X-rays. In this context, an X-ray of a set in a direction gives the number of points in the set on each line parallel to . For practical reasons, only X-rays in lattice directions, that is, directions parallel to a nonzero vector in the lattice, are permitted. By combining methods from algebraic number theory and convexity, we prove that there are four prescribed lattice directions such that convex subsets of (i.e., finite subsets with ) are determined, among all such sets, by their X-rays in these directions. We also show that three X-rays do not suffice for this purpose. This answers a question of Larry Shepp, and yields a stability result related to Hammer's X-ray problem. We further show that any set of seven prescribed mutually nonparallel lattice directions in have the property that convex subsets of are determined, among all such sets, by their X-rays in these directions. We also consider the use of orthogonal projections in the interactive technique of successive determination, in which the information from previous projections can be used in deciding the direction for the next projection. We obtain results for finite subsets of the integer lattice and also for arbitrary finite subsets of Euclidean space which are the best possible with respect to the numbers of projections used.

     

Development of practical syntheses of the marine anticancer agents discodermolide and dictyostatin

Initially isolated in trace quantities from deep-sea sponges, the structurally related polyketides discodermolide and dictyostatin share the same microtubule-stabilizing antimitotic mechanism as Taxol. Discodermolide has been the focus of intense research activity in order to develop a practical supply route, and these efforts ultimately allowed its large-scale synthesis and the initiation of clinical trials as a novel anticancer drug. Similarly, the re-isolation and synthesis of dictyostatin continues to stimulate the biological and chemical communities in their quest for the development of new chemotherapeutic agents. This comprehensive review chronicles the synthetic endeavours undertaken over the last 15 years towards the development and realization of practical chemical syntheses of discodermolide and, more recently, dictyostatin, focusing on the methods and strategies employed for achieving overall stereocontrol and key fragment unions, as well as the design and synthesis of novel hybrid structures.     

Development and validation of an LC-MS assay for finasteride and its application to prostate cancer prevention trial sample analysis

An analytical method is developed and validated for the quantitative determination of finasteride, a potent 5 alpha-reductase inhibitor, in human plasma. Calibration curves are linear in the concentration range of 1 to 100 ng/mL. Sample pretreatment involves a liquid-liquid extraction with ethyl acetate using 0.2 mL aliquots of plasma. Finasteride and the internal standard (beclomethasone) are separated on a Waters Symmetry Shield RP18 column (50 x 2.1 mm, 3.5 microm) and eluted using a gradient mobile phase composed of acetonitrile and 10mM ammonium acetate with 0.1% formic acid. The column eluant is monitored by mass spectrometry with electrospray ionization. A complete validation of the method is performed. For quality control samples at three different concentrations that were analyzed in quintuplicate, on six separate occasions, the accuracy and precision range from 95.2% to 101% and 3.4% to 7.3%, respectively. The developed method is subsequently applied to measure the steady state finasteride concentration of patients who participated in the Prostate Cancer Prevention Trial.     

Impact of proline and aspartic acid residues on the dissociation of intermolecularly crosslinked peptides

The dissociation of intermolecularly crosslinked peptides was evaluated for a series of peptides with proline or aspartic acid residues positioned adjacent to the crosslinking sites (lysine residues). The peptides were crosslinked with either disuccinimidyl suberate (DSS) or disuccinimidyl L-tartrate (DST), and the influence of proline and aspartic acid residues on the fragmentation patterns were investigated for precursor ions with and without a mobile proton. Collisionally activated dissociation (CAD) spectra of aspartic acid-containing crosslinked peptide ions, doubly-charged with both protons sequestered, were dominated by cleavage C-terminal to the Asp residue, similar to that of unmodified peptides. The proline-containing crosslinked peptides exhibited a high degree of internal ion formation, with the resulting product ions having an N-terminal proline residue. Upon dissociation of the doubly-charged crosslinked peptides, twenty to fifty percent of the fragment ion abundance was accounted for by multiple cleavage products. Crosslinked peptides possessing a mobile proton yielded almost a full series of b- and y-type fragment ions, with only proline-directed fragments still observed at high abundances. Interestingly, the crosslinked peptides exhibited a tendency to dissociate at the amide bond C-terminal to the crosslinked lysine residue, relative to the N-terminal side. One could envision updating computer algorithms to include these crosslinker specific product ions--particularly for precursor ions with localized protons--that provide complementary and confirmatory information, to offer more confident identification of both the crosslinked peptides and the location of the crosslink, as well as affording predictive guidelines for interpretation of the product-ion spectra of crosslinked peptides.     

Decongestion of methylene spectra in biological and non-biological systems using picosecond 2DIR spectroscopy measuring electron-vibration–vibration coupling

Methylene is found in the repeat units of many polymers including proteins. In some cases it appears to be a useful reporter of variation in local environment whilst in other contexts average behaviour seems to dominate. In this paper we apply a particular 2DIR technique to a range of systems containing methylene groups, showing that mode frequencies, linewidths and splittings can be easily extracted even when the infrared absorption bands are too congested to allow reliable analysis. 2DIR spectra of polyethylene and several liquid alkanes are compared and it is shown for the case of l-arginine that the methylene scissor modes are split and that this can be resolved by tracking the 2DIR spectrum as a function of time. Calculations from first principles reveal that for most of the methylene modes studied, electrical anharmonicity is the dominant contributor to the 2DIR cross-peak intensity, with the mechanical anharmonicity making only a small contribution.     

Assessment of the UVR protection provided by different tree species

In recent years, SunSmart campaigns have emphasized the importance of the use of shade as a strategy in the reduction of human exposure to solar UV radiation (UVR), particularly in early life with the provision of shade in schools. Trees can play an important role in shade provision, either as the main shade provider or to augment shade structures and increase UVR protection provided to the general population. A study to measure the protection provided by a range of trees common in Australian urban environments was undertaken during the summers of 2004/2005 and 2005/2006. Solar UVR beneath the trees was measured using UVR sensitive polysulphone badges positioned horizontally within the shaded area and were compared with those in full sunshine to give an indication of the protection provided. Measurements made on sunny days during the months of October to April indicated that the shade cover provided by the trees depended upon the tree species and changed with season as a result of changing foliage and sun angles. Measured protection factors ranged from 5 to 10 and were generally a maximum in the height of summer when the sun was highest in the sky and the foliage was densest.     

Reinvestigation of the electronic spectroscopy of the Au-Ar complex

The Au-Ar complex is reinvestigated employing resonance-enhanced multiphoton ionization spectroscopy. Spectra are reported, corresponding to the atomic transition Au(6p<--6s). This electronic excitation yields (2)Pi and (2)Sigma(+) states of Au-Ar, which interact under the influence of spin-orbit coupling. The spectra are consistent with strong sigma-pi mixing induced by the large spin-orbit coupling of Au, leading to strong interaction of the two Omega=12 states, which arise from the Ar((1)S(0))+Au((2)P(12,32)) asymptotes, and the consequent formation of a "shelf" on the outer wall of the lowest Omega=12 state. In addition, high-level ab initio calculations are reported on the ground electronic state, X (2)Sigma(+), including extrapolation to the basis set limit.