Activity determination without tracers in high-resolution alpha-particle spectrometry

High-resolution alpha spectrometry was applied for the activity determination of 10 reference sources containing different amounts of ²³⁸Pu, ²³⁹Pu, ²⁴⁰Pu and ²⁴²Pu. They were analyzed as blind sources using a novel spectrum analysis tool ADAM. The information needed in the spectrum unfolding was taken only from the spectrum under investigation, and no tracers were applied. Therefore, a Monte Carlo program AASI was used to compute geometrical detection efficiency of the measurement setup. All reported activities corresponded to those of the reference sources within expanded uncertainty. The developed tools can be used for the activity determination in nondestructive alpha spectrometry or when the radionuclide composition does not change during the sample processing.     

Dual representation of superhedging costs in illiquid markets

This paper studies superhedging of contingent claims in illiquid markets where trading costs may depend nonlinearly on the traded amounts and portfolios may be subject to constraints. We give dual expressions for superhedging costs of financial contracts where claims and premiums are paid possibly at multiple points in time. Besides classical pricing problems, this setup covers various swap and insurance contracts where premiums are paid in sequences. Validity of the dual expressions is proved under new relaxed conditions related to the classical no-arbitrage condition. A new version of the fundamental theorem of asset pricing is given for unconstrained models with nonlinear trading costs.     

Generalized Mann iterates for constructing fixed points in Hilbert spaces

The mean iteration scheme originally proposed by Mann is extended to a broad class of relaxed, inexact fixed point algorithms in Hilbert spaces. Weak and strong convergence results are established under general conditions on the underlying averaging process and the type of operators involved. This analysis significantly widens the range of applications of mean iteration methods. Several examples are given.     

Hexanol-induced order-disorder transitions in lamellar self-assembling aggregates of bacteriochlorophyll c in Chlorobium tepidum chlorosomes

Chlorosomes are light-harvesting complexes of green photosynthetic bacteria. Chlorosomes contain bacteriochlorophyll (BChl) c, d, or e aggregates that exhibit strong excitonic coupling. The short-range order, which is responsible for the coupling, has been proposed to be augmented by pigment arrangement into undulated lamellar structures with spacing between 2 and 3 nm. Treatment of chlorosomes with hexanol reversibly converts the aggregated chlorosome chlorophylls into a form with spectral properties very similar to that of the monomer. Although this transition has been extensively studied, the structural basis remains unclear due to variability in the obtained morphologies. Here we investigated hexanol-induced structural changes in the lamellar organization of BChl c in chlorosomes from Chlorobium tepidum by a combination of X-ray scattering, electron cryomicroscopy, and optical spectroscopy. At a low hexanol/pigment ratio, the lamellae persisted in the presence of hexanol while the short-range order and exciton interactions between chlorin rings were effectively eliminated, producing a monomer-like absorption. The result suggested that hexanol hydroxyls solvated the chlorin rings while the aliphatic tail partitioned into the hydrophobic part of the lamellar structure. This partitioning extended the chlorosome along its long axis. Further increase of the hexanol/pigment ratio produced round pigment-hexanol droplets, which lost all lamellar order. After hexanol removal the spectral properties were restored. In the samples treated under the high hexanol/pigment ratio, lamellae reassembled in small domains after hexanol removal while the shape and long-range order were irreversibly lost. Thus, all the interactions required for establishing the short-range order by self-assembly are provided by BChl c molecules alone. However, the long-range order and overall shape are imposed by an external structure, e.g., the proteinaceous chlorosome baseplate.     

A density functional theory (DFT) and time-dependent density functional theory (TDDFT) study on optical transitions in oligo(p-phenylenevinylene)-fullerene dyads and the applicability to resonant energy transfer

The optical transitions of three different size oligo(p-phenylenevinylene)-fullerene dyads (OPV(n)-MPC(60); n = 2-4) and of the corresponding separate molecules are studied using density functional theory (DFT) and time-dependent density functional theory. The DFT is used to determine the geometries and the electronic structures of the ground states. Transition energies and excited-state structures are obtained from the TDDFT calculations. Resonant energy transfer from OPV(n) to MPC(60) is also studied and the Fermi golden rule is used, along with two simple models to describe the electronic coupling to calculate the energy transfer rates. The hybrid-type PBE0 functional is used with a split-valence basis set augmented with a polarization function (SV(P)) in calculations and the calculated results are compared to the corresponding experimental results. The calculated PBE0 spectra of the OPV(n)-MPC(60) dyads correspond to the experimental spectra very well and are approximately sums of the absorption spectra of the separate OPV(n) and MPC(60) molecules. Also, the absorption energies of OPV(n) and MPC(60) and the emission energies of OPV(n) are predicted well with the PBE0 functional. The PBE0 calculated resonant energy transfer rates are in a good agreement with the experimental rates and show the existence of many possible pathways for energy transfer from the first excited singlet states of the OPV(n) molecules to the MPC(60) molecule.     

Hollow nanoparticle nanotubes with a nanoscale brick wall structure of clay mineral platelets

Long hollow inorganic nanoparticle nanotubes have been synthesized by templating of block copolymer electrospun fibers with clay mineral platelets followed by interlinking of the platelets using condensation reactions.     

Structure and Bonding in Bis(1‐naphthyl) Diselenide and Bis{[2‐(N,N‐dimethylamino)methyl]phenyl} Tetraselenide,and Their Brominated Derivatives

The formation and crystal structures of bis(1‐naphthyl) diselenide ( 1 ) and bis{[2‐(N,N‐dimethylamino)methyl]phenyl} tetraselenide ( 2 ) are described. Whereas 1 can be produced in good yields, 2 is formed only as a minor product together with the known main product, bis{[2‐(N,N‐dimethylamino)methyl]phenyl} diselenide. The composition of the reaction mixture is semi‐quantitatively estimated by ⁷⁷Se NMR spectroscopy and DFT calculations. The effect of the n²→σ*(Se–Se) and π→σ*(Se–Se) secondary bonding interactions on the Se–Se bonds is discussed both by DFT calculations and comparison with literature, as available. The bromination of 1 yields monomeric (1‐naphthyl)selenenyl bromide ( 3 ) in good yields. That of the reaction mixture of (C₆H₄CH₂NMe₂)Se_x (x = 2–4) and Se₈ afforded (C₆H₄CH₂NMe₂H)₂[SeBr₄] ( 4 ) and (C₆H₄CH₂NMe₂H)₂[SeBr₆] ( 5 ) in addition to (C₆H₄CH₂NMe₂)SeBr, which has been previously reported.     

A microfabricated micropillar liquid chromatographic chip monolithically integrated with an electrospray ionization tip

We present the first monolithically integrated silicon/glass liquid chromatography-electrospray ionization microchip for mass spectrometry. The microchip is fabricated by bonding a silicon wafer, which has deep reactive ion etched micropillar-filled channels, together with a glass lid. Both the silicon channel and the glass lid have a through-wafer etched sharp tip that produces a stable electrospray. The microchip is also compatible with laser induced fluorescence (LIF) detection, due to the glass lid. Separation of drugs in less than 5 minutes using either SiO(2) (normal phase) or C(18) coated (reversed-phase) pillars with good sensitivity was demonstrated with mass spectrometric detection as well as separation of fluorescent compounds with LIF detection.     

Estimating head-related transfer functions of human subjects from pressure-velocity measurements

Direct measurements of individual head-related transfer functions (HRTFs) with a probe microphone at the eardrum are unpleasant, risky, and unreliable and therefore have not been widely used. Instead, the HRTFs are commonly measured from the blocked ear canal entrance, which excludes the effects of the individual ear canals and eardrums. This paper presents a method that allows obtaining individually correct magnitude frequency responses of HRTFs at the eardrum from pressure-velocity (PU) measurements at the ear canal entrance with a miniature PU sensor. The HRTFs of 25 test subjects with nine directions of sound incidence were estimated using real anechoic measurements and an energy-based estimation method. To validate the approach, measurements were also conducted with probe microphones near the eardrums as well as at blocked ear canal entrances. Comparisons between the different methods show that the method presented is a valid and reliable technique for obtaining magnitude frequency responses of HRTFs. The HRTF filters designed using the PU measurements are also shown to yield more correct frequency responses at the eardrum than the filters designed using measurements from the blocked ear canal entrance.     

Polarised bidirectional reflectance factor measurements from soil, stones, and snow

The bidirectional reflectance factor and degree of linear polarisation of selected snow, soil, and gravel types have been measured using Finnish geodetic institute field goniospectropolariphotometer (FIGIFIGO). It was observed that with all measured samples the degree of linear polarisation is weakest 0–30 backwards from nadir, turning 1–5% negative in the backward direction, and growing larger (5–50%) in the forward and Brewster directions. Polarisation was found to be inversely but non-linearly proportional to reflectance. In addition, a wavelength-dependent trend was found to exist in some data, but in general, the wavelength dependence was smooth. Dry old snow polarises clearly more than melting snow or new snow. White gravel polarises somewhat similarly to snow in visible region, and black gravel resembles snow in infrared.The authors conclude that polarisation observations may be useful in land surface remote sensing, but that only far-forward angles (60–70) contain a strong enough signal for easy interpretation. The polarisation spectrum brings little additional information to reflection spectrum, but in conditions where the reflectance spectrum cannot be accurately normalised or incident irradiation is not known, polarisation spectrum could still be usable. The directional signal is strong and may yield refractive index or microstructure, and must be understood in any application. Polarisation near nadir is low for all known samples, and can thus be safely ignored with most non-polarised imaging applications. However, for accurate atmospheric polarimetry, e.g. by polarisation and directionality of the earth's reflectances (POLDER) or aerosol polarimetry sensor (APS) sensors, it is recommended to take into account land surface polarisation.