A new governance perspective on port–hinterland relationships: the Port Hinterland Impact (PHI) matrix

We develop a new governance perspective on port–hinterland linkages and related port impacts. Many stakeholders in a port’s hinterland now demand tangible economic benefits from port activities, as a precondition for supporting port expansion and infrastructural investments. We use a governance lens to assess this farsighted contracting challenge. We find that most contemporary economic impact assessments of port investment projects pay scant attention to the contractual relationship challenges in port-hinterland relationships. In contrast, we focus explicitly on the spatial distribution of such impacts and the related contractual relationship issues facing port authorities or port users and their stakeholders in the port hinterland. We introduce a new concept, the Port Hinterland Impact (PHI) matrix, which focuses explicitly on the spatial distribution of port impacts and related contractual relationship challenges. The PHI matrix offers insight into port impacts using two dimensions: logistics dedicatedness, as an expression of Williamsonian asset specificity in the sphere of logistics contractual relationships, and geographic reach, with a longer reach typically reflecting the need for more complex contacting to overcome ‘distance’ challenges with external stakeholders. We use the PHI matrix in our empirical, governance-based analysis of contractual relationships between the port authorities in Antwerp and Zeebrugge, and their respective stakeholders.

Stocking may increase mitochondrial DNA diversity but fails to halt the decline of endangered Atlantic salmon populations

Over the last 50 years, Spanish Atlantic salmon (Salmo salar) populations have been in decline. In order to bolster these populations, rivers were stocked with fish of northern European origin during the period 1974-1996, probably also introducing the furunculosis-inducing pathogen, Aeromonas salmonicida. Here we assess the relative importance of processes influencing mitochondrial (mt)DNA variability in these populations from 1948 to 2002. Genetic material collected over this period from four rivers in northern Spain (Cantabria) was used to detect variability at the mtDNA ND1 gene. Before stocking, a single haplotype was found at high frequency (0.980). Following stocking, haplotype diversity (h) increased in all rivers (mean h before stocking was 0.041, and 0.245 afterwards). These increases were due principally to the dramatic increase in frequency of a previously very low frequency haplotype, reported at higher frequencies in northern European populations proximate to those used to stock Cantabrian rivers. Genetic structuring increased after stocking: among-river differentiation was low before stocking (1950s/1960s Phi(ST) = -0.00296-0.00284), increasing considerably at the height of stocking (1980s Phi(ST) = 0.18932) and decreasing post-stocking (1990s/2002 Phi(ST) = 0.04934-0.03852). Gene flow from stocked fish therefore seems to have had a substantial role in increasing mtDNA variability. Additionally, we found significant differentiation between individuals that had probably died from infectious disease and apparently healthy, angled fish, suggesting a possible role for pathogen-driven selection of mtDNA variation. Our results suggest that stocking with non-native fish may increase genetic diversity in the short term, but may not reverse population declines.

Stabilization of two smallest possible diastereomeric beta-hairpins in a water soluble tetrapeptide containing non-coded alpha-amino isobutyric acid (Aib) and m-amino benzoic acid

Single crystal X-ray diffraction study reveals that the water soluble tetrapeptide H2N-Ile-Aib-Leu-m-ABA-CO2H, containing non-coded Aib (alpha-amino isobutyric acid) and m-ABA (meta-amino benzoic acid), crystallizes with two smallest possible diastereomeric beta-hairpin molecules in the asymmetric unit. Although in both of the molecules the chiralities at Ile(1) and Leu(3) are S, a conformational reversal in the back bone chain is observed to produce the beta-hairpins with beta-turn conformations of type II and II'. Interestingly Aib which is known to adopt helical conformation, adopts unusual semi-extended conformation with phi: -49.5(5)degrees, psi: 135.2(5)degrees in type II and phi: 50.6(6)degrees. psi: -137.0(4)degrees in type II' for occupying the i + 1 position of the beta-turns. The two hairpin molecules are further interlocked through intermolecular hydrogen bonds and electrostatic interactions between CO2- and -+NH3 groups to form dimeric supramolecular beta-hairpin aggregate in the crystal state. The CD measurement and 2D NMR study of the peptide in aqueous medium support the existence of beta-hairpin structure in water. (C) 2009 Elsevier B.V. All rights reserved.

Photochemical, photophysical and redox properties of novel fulgimide derivatives with attached 2,2 '-bipyridine (bpy) and [M(bpy)(3)](2+) (M = Ru and Os) moieties

Fulgimides monosubstituted with [M(bpy)(3)](2+) (M = Ru, Os; bpy = 2,2'-bipyridine) chromophore units and with a single bpy group were synthesized and investigated as components of conceivable dinuclear photochromic switches of luminescence. The E-, Z- and closed-ring (C) photoisomer forms of the bpy-bound fulgimide were successfully separated by semi-preparative HPLC. The same procedure failed, however, in the case of the [M(bpy)(3)](2+)-substituted fulgimides. Energy transfer from the excited photochromic unit to the metal-bpy centre competes with the fulgimide cyclization, reducing the photocyclization quantum yields by approximately one order of magnitude compared to the non-complexed fulgimide-bpy ligand (phi(EC) = 0.17, phi(EZ) = 0.071, phi(ZE) = 0.15 at lambda(exc) = 334 nm). The cycloreversion of the fulgimide-bpy ligand is less efficient (phi(CE) = 0.047 at lambda(exc) = 520 nm). The intensity of the (MLCT)-M-3-based luminescence of the metal-bpy chromophore (in MeCN, phi(deaer) = 6.6 x 10(-2) and tau(deaer) = 1.09 mu s for Ru; phi(deaer) = 6.7 x 10(-3) and tau(deaer) = 62 ns for Os) is not affected by the fulgimide photoconversion. These results and supporting spectro-electrochemical data reveal that the lowest triplet excited states of the photochromic fulgimide moiety in all its E-, Z- and closed-ring forms lie above the lowest 3MLCT levels of the attached ruthenium and osmium chromophores. The actual components are therefore unlikely to form a triad acting as functional switch of energy transfer from [Ru(bpy)(3)](2+) to [Os(bpy)(3)](2+) through the photochromic fulgimide bridge.

DNA cleavage and antitumour activity of platinum(II) and copper(II) compounds derived from 4-methyl-2-N-(2-pyridylmethyl)aminophenol: spectroscopic, electrochemical and biological investigation

The reaction of the redox-active ligand, Hpyramol (4-methyl-2-N-(2-pyridylmethyl)aminophenol) with K2PtCl4 yields monofunctional square-planar [Pt(pyrimol)Cl], PtL-Cl, which was structurally characterised by single-crystal X-ray diffraction and NMR spectroscopy. This compound unexpectedly cleaves supercoiled double-stranded DNA stoichiometrically and oxidatively, in a non-specific manner without any external reductant added, under physiological conditions. Spectro-electrochemical investigations of PtL-Cl were carried out in comparison with the analogue CuL-Cl as a reference compound. The results support a phenolate oxidation, generating a phenoxyl radical responsible for the ligand-based DNA cleavage property of the title compounds. Time-dependent in vitro cytotoxicity assays were performed with both PtL-Cl and CuL-Cl in various cancer cell lines. The compound CuL-Cl overcomes cisplatin-resistance in ovarian carcinoma and mouse leukaemia cell lines, with additional activity in some other cells. The platinum analogue, PtL-Cl also inhibits cell-proliferation selectively. Additionally, cellular-uptake studies performed for both compounds in ovarian carcinoma cell lines showed that significant amounts of Pt and Cu were accumulated in the A2780 and A2780R cancer cells. The conformational and structural changes induced by PtL-Cl and CuL-Cl on calf thymus DNA and phi X174 supercoiled phage DNA at ambient conditions were followed by electrophoretic mobility assay and circular dichroism spectroscopy. The compounds induce extensive DNA degradation and unwinding, along with formation of a monoadduct at the DNA minor groove. Thus, hybrid effects of metal-centre variation, multiple DNA-binding modes and ligand-based redox activity towards cancer cell-growth inhibition have been demonstrated. Finally, reactions of PtL-Cl with DNA model bases (9-Ethylguanine and 5'-GMP) followed by NMR and MS showed slow binding at Guanine-N7 and for the double stranded self complimentary oligonucleotide d(GTCGAC)(2) in the minor groove.

Cardiac Na+/H+ exchanger during post-natal development in the rat: Changes in mRNA expression and sarcolemmal activity

We examined Na+–H+exchanger isoform 1 (NHE-1) mRNA expression in ventricular myocardium and its correlation with sarcolemmal NHE activity in isolated ventricular myocytes, during postnatal development in the rat. The expression of glyceraldehyde-3-phosphate dehydrogenase (GAPDH) mRNA did not change in ventricular myocardium between 2 and 42 days after birth. Therefore, at seven time points within that age range, GAPDH expression was used to normalize NHE-1 mRNA levels, as determined by reverse transcription polymerase chain reaction analysis. There was a progressive five-fold reduction in NHE-1 mRNA expression in ventricular myocardium from 2 days to 42 days of age. As an index of NHE activity, acid efflux rates (JH) were determined in single neonatal (2–4-day-old) and adult (42-day-old) ventricular myocytes (n=16/group) loaded with the pH fluoroprobe carboxy-seminaphthorhodafluor-1. In HEPES-buffered medium, basal intracellular pH (pHi) was similar at 7.28±0.02 in neonatal and 7.31±0.02 in adult myocytes, but intrinsic buffering power was lower in the former age group. The rate at which pHirecovered from a similar acid load was significantly greater in neonatal than in adult myocytes (0.36±0.07v0.16±0.02 pH units/min at pHi=6.8). This was reflected by a significantly greaterJH(22±4v9±1 pmol/cm2/s at pHi=6.8), indicating greater sarcolemmal NHE activity in neonatal myocytes. The concomitant reductions in tissue NHE-1 mRNA expression and sarcolemmal NHE activity suggest that myocardial NHE-1 is subject to regulation at the mRNA level during postnatal development.

Double-gyroid morphology of a polystyrene-block-poly(ferrocenylethylmethylsilane) diblock copolymer: a route to ordered bicontinuous nanoscale architectures

A polystyrene-block-poly(ferrocenylethylmethylsilane) diblock copolymer, displaying a double-gyroid morphology when self-assembled in the solid state, has been prepared with a PFEMS volume fraction phi(PFMS)=0.39 and a total molecular weight of 64 000 Da by sequential living anionic polymerisation. A block copolymer with a metal-containing block with iron and silicon in the main chain was selected due to its plasma etch resistance compared to the organic block. Self-assembly of the diblock copolymer in the bulk showed a stable, double-gyroid morphology as characterised by TEM. SAXS confirmed that the structure belonged to the Ia3d space group.

The persistence of solar activity indicators and the descent of the sun into Maunder Minimum conditions

The recent low and prolonged minimum of the solar cycle, along with the slow growth in activity of the new cycle, has led to suggestions that the Sun is entering a Grand Solar Minimum (GSMi), potentially as deep as the Maunder Minimum (MM). This raises questions about the persistence and predictability of solar activity. We study the autocorrelation functions and predictability R^2_L(t) of solar indices, particularly group sunspot number R_G and heliospheric modulation potential phi for which we have data during the descent into the MM. For R_G and phi, R^2_L (t) > 0.5 for times into the future of t = 4 and 3 solar cycles, respectively: sufficient to allow prediction of a GSMi onset. The lower predictability of sunspot number R_Z is discussed. The current declines in peak and mean R_G are the largest since the onset of the MM and exceed those around 1800 which failed to initiate a GSMi.

Approximate solution of second kind integral equations on infinite cylindrical surfaces

The paper considers second kind integral equations of the form $\phi (x) = g(x) + \int_S {k(x,y)} \phi (y)ds(y)$ (abbreviated $\phi = g + K\phi $), in which S is an infinite cylindrical surface of arbitrary smooth cross section. The “truncated equation” (abbreviated $\phi _a = E_a g + K_a \phi _a $), obtained by replacing S by $S_a $, a closed bounded surface of class $C^2 $, the boundary of a section of the interior of S of length $2a$, is also discussed. Conditions on k are obtained (in particular, implying that K commutes with the operation of translation in the direction of the cylinder axis) which ensure that $I - K$ is invertible, that $I - K_a $ is invertible and $(I - K_a )^{ - 1} $ is uniformly bounded for all sufficiently large a, and that $\phi _a $ converges to $\phi $ in an appropriate sense as $a \to \infty $. Uniform stability and convergence results for a piecewise constant boundary element collocation method for the truncated equations are also obtained. A boundary integral equation, which models three-dimensional acoustic scattering from an infinite rigid cylinder, illustrates the application of the above results to prove existence of solution (of the integral equation and the corresponding boundary value problem) and convergence of a particular collocation method.

On the (un)-ambiguity of adjectival modification in Spanish determiner phrases: informing debates on the mental representations of L2 syntax.

This study contributes to a central debate within contemporary generative second language (L2) theorizing: the extent to which adult learners are (un)able to acquire new functional features that result in a L2 grammar that is mentally structured like the native target (see White, 2003). The adult acquisition of L2 nominal phi-features is explored, with focus on the syntactic and semantic reflexes in the related domain of adjective placement in two experimental groups: English-speaking intermediate (n = 21) and advanced (n = 24) learners of Spanish, as compared to a native-speaker control group (n = 15). Results show that, on some of the tasks, the intermediate L2 learners appear to have acquired the syntactic properties of the Spanish determiner phrase but, on other tasks, to show some delay with the semantic reflexes of prenominal and postnominal adjectives. Crucially, however, our data demonstrate full convergence by all advanced learners and thus provide evidence in contra the predictions of representational deficit accounts (e.g., Hawkins & Chan, 1997; Hawkins & Franceschina, 2004; Hawkins & Hattori, 2006).

Default perception of high-speed motion

When human observers are exposed to even slight motion signals followed by brief visual transients—stimuli containing no detectable coherent motion signals—they perceive large and salient illusory jumps. This novel effect, which we call “high phi”, challenges well-entrenched assumptions about the perception of motion, namely the minimal-motion principle and the breakdown of coherent motion perception with steps above an upper limit. Our experiments with transients such as texture randomization or contrast reversal show that the magnitude of the jump depends on spatial frequency and transient duration, but not on the speed of the inducing motion signals, and the direction of the jump depends on the duration of the inducer. Jump magnitude is robust across jump directions and different types of transient. In addition, when a texture is actually displaced by a large step beyond dmax, a breakdown of coherent motion perception is expected, but in the presence of an inducer observers again perceive coherent displacements at or just above dmax. In sum, across a large variety of stimuli, we find that when incoherent motion noise is preceded by a small bias, instead of perceiving little or no motion, as suggested by the minimal-motion principle, observers perceive jumps whose amplitude closely follows their own dmax limits.

The projected hand illusion: component structure in a community sample, and association with demographics, cognition and psychotic-like experiences

The projected hand illusion (PHI) is a variant of the rubber hand illusion (RHI), and both are commonly used to study mechanisms of self-perception. A questionnaire was developed by Longo et al. (2008) to measure qualitative changes in the RHI. Such psychometric analyses have not yet been conducted on the questionnaire for the PHI. The present study is an attempt to validate minor modifications of the questionnaire of Longo et al. to assess the PHI in a community sample (n = 48) and to determine the association with selected demographic (age, sex, years of education), cognitive (Digit Span), and clinical (psychotic-like experiences) variables. Principal components analysis on the questionnaire data extracted four components: Embodiment of “Other” Hand, Disembodiment of Own Hand, Deafference, and Agency—in both synchronous and asynchronous PHI conditions. Questions assessing “Embodiment” and “Agency” loaded onto orthogonal components. Greater illusion ratings were positively associated with being female, being younger, and having higher scores on psychotic-like experiences. There was no association with cognitive performance. Overall, this study confirmed that self-perception as measured with PHI is a multicomponent construct, similar in many respects to the RHI. The main difference lies in the separation of Embodiment and Agency into separate constructs, and this likely reflects the fact that the “live” image of the PHI presents a more realistic picture of the hand and of the stroking movements of the experimenter compared with the RHI.

Structure and magnetic properties of polydisperse ferrofluids: a molecular dynamics study

We study by Langevin molecular dynamics simulations systematically the influence of polydispersity in the particle size, and subsequently in the dipole moment, on the physical properties of ferrofluids. The polydispersity is in a first approximation modeled by a bidisperse system that consists of small and large particles at different ratios of their volume fractions. In the first part of our investigations the total volume fraction of the system is fixed, and the volume fraction phi(L) of the large particles is varied. The initial susceptibility chi and magnetization curve of the systems show a strong dependence on the value of phi(L). With the increase of phi(L), the magnetization M of the system has a much faster increment at weak fields, and thus leads to a larger chi. We performed a cluster analysis that indicates that this is due to the aggregation of the large particles in the systems. The average size of these clusters increases with increasing phi(L). In the second part of our investigations, we fixed the volume fraction of the large particles, and increased the volume fraction phi(S) of the small particles in order to study their influence on the chain formation of the large ones. We found that the average aggregate size formed by large particles decreases when phi(S) is increased, demonstrating a significant effect of the small particles on the structural properties of the system. A topological analysis of the structure reveals that the majority of the small particles remain nonaggregated. Only a small number of them are attracted to the ends of the chains formed by large particles.

Dynamic response times of electrorheological fluids in steady shear

Transient responses of electrorheological fluids to square-wave electric fields in steady shear are investigated by computational simulation method. The structure responses of the fluids to the field with high frequency are found to be very similar to that to the field with very low frequency or the sudden applied direct current field. The stress rise processes are also similar in both cases and can be described by an exponential expression. The characteristic time tau of the stress response is found to decrease with the increase of the shear rate (gamma) over dot and the area fraction of the particles phi(2). The relation between them can be roughly expressed as tau proportional to(gamma) over dot(-3/4)phi(2)(-3/2). The simulation results are compared with experimental measurements. The aggregation kinetics of the particles in steady shear is also discussed according to these results.

Long term changes in EUV and X-ray emissions from the solar corona and chromosphere as measured by the response of the Earth’s ionosphere during total solar eclipses from 1932 to 1999

Measurements of the ionospheric E region during total solar eclipses in the period 1932-1999 have been used to investigate the fraction of Extreme Ultra Violet and soft X-ray radiation, phi, that is emitted from the limb corona and chromosphere. The relative apparent sizes of the Moon and the Sun are different for each eclipse, and techniques are presented which correct the measurements and, therefore, allow direct comparisons between different eclipses. The results show that the fraction of ionising radiation emitted by the limb corona has a clear solar cycle variation and that the underlying trend shows this fraction has been increasing since 1932. Data from the SOHO spacecraft are used to study the effects of short-term variability and it is shown that the observed long-term rise in phi has a negligible probability of being a chance occurrence.