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Recent research has shown that the early lexical representations children establish in their second year of life already seem to be phonologically detailed enough to allow differentiation from very similar forms. In contrast to these findings children with specific language impairment show problems in discriminating phonologically similar word forms up to school age. In our study we investigated the question whether there would be differences in the processing of phonological details in normally developing and in children with low language performance in the second year of life. This was done by a retrospective study in which in the processing of phonological details was tested by a preferential looking experiment when the children were 19 months old. At the age of 30 months children were tested with a standardized German test of language comprehension and production (SETK2). The preferential looking data at 19 months revealed an opposite reaction pattern for the two groups: while the children scoring normally in the SETK2 increase their fixations of a pictured object only when it was named with the correct word, children with later low language performance did so only when presented with a phonologically slightly deviant mispronunciation. We suggest that this pattern does not point to a specific deficit in processing phonological information in these children but might be related to an instability of early phonological representations, and/or a generalized problem of information processing as compared to typically developing children.
Recent work has shown that English-learning 18-month-olds can detect the relationship between discontinuous morphemes such as is and -ing in Grandma is always running (Gomez, 2002; Santelmann & Jusczyk, 1998) but only at a maximum of 3 intervening syllables. In this article we examine the tracking of discontinuous dependencies in children acquiring German. Due to freer word order, German allows for greater distances between dependent elements and a greater syntactic variety of the intervening elements than English does. The aim of this study was to investigate whether factors other than distance may influence the child’s capacity to recognize discontinuous elements. Our findings provide evidence that children’s recognition capacities are affected not only by distance but also by their ability to linguistically analyze the material intervening between the dependent elements. We speculate that this result supports the existence of processing mechanisms that reduce a discontinuous relation to a local one based on subcategorization relations.
How do children determine the syntactic category of novel words? In this article we present the results of 2 experiments that investigated whether German children between 12 and 16 months of age can use distributional knowledge that determiners precede nouns and subject pronouns precede verbs to syntactically categorize adjacent novel words. Evidence from the head-turn preference paradigm shows that, although 12- to 13-month-olds cannot do this, 14- to 16-month-olds are able to use a determiner to categorize a following novel word as a noun. In contrast, no categorization effect was found for a novel word following a subject pronoun. To understand this difference we analyzed adult child-directed speech. This analysis showed that there are in fact stronger co-occurrence relations between determiners and nouns than between subject pronouns and verbs. Thus, in German determiners may be more reliable cues to the syntactic category of an adjacent novel word than are subject pronouns. We propose that the capacity to syntactically categorize novel words, demonstrated here for the first time in children this young, mediates between the recognition of the specific morphosyntactic frame in which a novel word appears and the word-to-world mapping that is needed to build up a semantic representation for the novel word.
Many methods have been proposed for the simulation of constrained mechanical systems. The most obvious of these have mild instabilities and drift problems. Consequently, stabilization techniques have been proposed A popular stabilization method is Baumgarte's technique, but the choice of parameters to make it robust has been unclear in practice. Some of the simulation methods that have been proposed and used in computations are reviewed here, from a stability point of view. This involves concepts of differential-algebraic equation (DAE) and ordinary differential equation (ODE) invariants. An explanation of the difficulties that may be encountered using Baumgarte's method is given, and a discussion of why a further quest for better parameter values for this method will always remain frustrating is presented. It is then shown how Baumgarte's method can be improved. An efficient stabilization technique is proposed, which may employ explicit ODE solvers in case of nonstiff or highly oscillatory problems and which relates to coordinate projection methods. Examples of a two-link planar robotic arm and a squeezing mechanism illustrate the effectiveness of this new stabilization method.
A Hamiltonian system in potential form (formula in the original abstract) subject to smooth constraints on q can be viewed as a Hamiltonian system on a manifold, but numerical computations must be performed in Rn. In this paper methods which reduce "Hamiltonian differential algebraic equations" to ODEs in Euclidean space are examined. The authors study the construction of canonical parameterizations or local charts as well as methods based on the construction of ODE systems in the space in which the constraint manifold is embedded which preserve the constraint manifold as an invariant manifold. In each case, a Hamiltonian system of ordinary differential equations is produced. The stability of the constraint invariants and the behavior of the original Hamiltonian along solutions are investigated both numerically and analytically.
Many methods have been proposed for the stabilization of higher index differential-algebraic equations (DAEs). Such methods often involve constraint differentiation and problem stabilization, thus obtaining a stabilized index reduction. A popular method is Baumgarte stabilization, but the choice of parameters to make it robust is unclear in practice. Here we explain why the Baumgarte method may run into trouble. We then show how to improve it. We further develop a unifying theory for stabilization methods which includes many of the various techniques proposed in the literature. Our approach is to (i) consider stabilization of ODEs with invariants, (ii) discretize the stabilizing term in a simple way, generally different from the ODE discretization, and (iii) use orthogonal projections whenever possible. The best methods thus obtained are related to methods of coordinate projection. We discuss them and make concrete algorithmic suggestions.
An approach to the development of fluorescent probes to follow polymerizations in situ using fluorinated cross-conjugated enediynes (Y-enynes) is reported. Different substitution patterns in the Y-enynes result in distinct solvatochromic behavior. β,β-Bis(phenylethynyl)pentafluorostyrene 7, which bears no donor substituents and only fluorine at the styrene moiety, shows no solvatochromism. Donor substituted β,β-bis(3,4,5-trimethoxyphenylethynyl) pentafluorostyrene 8 and β,β-bis(4-butyl-2,3,5,6-tetrafluorophenylethynyl)-3,4,5-trimethoxystyrene 9 exhibit solvatochromism upon change of solvent polarity. Y-enyne 8 showed the largest solvatochromic shift (94 nm bathochromic shift) upon changing solvent from cyclohexane to acetonitrile. A smaller solvatochromic response (44 nm bathochromic shift) was observed for 9. Lippert–Mataga treatment of 8 and 9 yields slopes of -10,800 and -6,400 cm -1, respectively. This corresponds to a change in dipole moment of 9.6 and 6.9 D, respectively. The solvatochromic behavior in 8 and 9 supports the formation of an intramolecular charge transfer (ICT) state. The low fluorescence quantum yields are caused by competitive double bond rotation. The fluorescence decay time of 9 decreases in methyltetrahydrofuran from 2.1 ns at 77 K to 0.11 ns at 200 K. Efficient single bond rotation in 9 was frozen at -50 °C in a configuration in which the trimethoxyphenyl ring is perpendicular to the fluorinated rings. 7–9 are photostable compounds. The X-ray structure of 7 shows it is not planar and that its conjugation is distorted. Y-enyne 7 stacks in the solid state showing coulombic, actetylene–arene, and fluorine–π interactions.
Investigations with frequency domain photon density waves allow elucidation of absorption and scattering properties of turbid media. The temporal and spatial propagation of intensity modulated light with frequencies up to more than 1 GHz can be described by the P1 approximation to the Boltzmann transport equation. In this study, we establish requirements for the appropriate choice of turbid model media and characterize mixtures of isosulfan blue as absorber and polystyrene beads as scatterer. For these model media, the independent determination of absorption and reduced scattering coefficients over large absorber and scatterer concentration ranges is demonstrated with a frequency domain photon density wave spectrometer employing intensity and phase measurements at various modulation frequencies.
First studies of electron transfer in [N]phenylenes were performed in bimolecular quenching reactions of angular [3]- and triangular [4]phenylene with various electron acceptors. The relation between the quenching rate constants kq and the free energy change of the electron transfer (ΔG0CS ) could be described by the Rehm-Weller equation. From the experimental results, a reorganization energy λ of 0.7 eV was derived. Intramolecular electron transfer reactions were studied in an [N]phenylene bichomophore and a corresponding reference compound. Fluorescence lifetime and quantum yield of the bichromophor display a characteristic dependence on the solvent polarity, whereas the corresponding values of the reference compound remain constant. From the results, a nearly isoenergonic ΔG0CS can be determined. As the triplet quantum yield is nearly independent of the polarity, charge recombination leads to the population of the triplet state.
The end of the cold war division of the Baltic Sea in 1989, and the three Baltic states’ return to independence in 1991 created new opportunities for the decision-makers of the area, as well as new possibilities for fashioning security in the region. This article will examine the security debate affecting the Baltic Sea region in the post-cold war period, and in particular, the relevance of the European Union to that debate. The following section will examine various concepts of security relevant to the Baltic region; the third section looks at the EU and the Baltic area; and the last part deals with the implications that EU membership by the Baltic Sea states may have for the security of the Baltic Sea zone.
The article mobilises the concept of strategic culture in order to identify the impact of history upon contemporary security policy. The article will first look at the "wholesale construction" of a strategic culture after the Second World War in West Germany before exploring its impact upon security policy since the end of the Cold War in two areas: the Bundeswehr's out-of-area role and conscription. The central argument presented here is that the strategic culture of the former Federal Republic now writ large on to the new united Germany sets the context within which security policies are designed. This strategic culture, as will be argued, acts as both a facilitating and a restraining variable on behaviour, making certain policy options possible and others impossible.
Observers of international politics have been conscious of the growing international involvement of non-central governments (NCGs), particularly in federal systems. These have been supplemented by the internationalisation of subnational actors in quasi-federal and even unitary states. One of the difficulties is that analysis has often been locked into the dominant paradigm debate in International Relations concerning who and who are not significant actors. Having briefly explored the nature of this changing environment, marked by a growing emphasis on access rather than control as a policy objective and the emergence of what is termed a 'catalytic diplomacy', the discussion focuses on the need for linkage between the levels of government in the pursuit of international as well as domestic policy goals. The nature of linkage mechanisms are discussed.
Improvement of a fluorescence immunoassay with a compact diode-pumped solid state laser at 315 nm
(2006)
We demonstrate the improvement of fluorescence immunoassay (FIA) diagnostics in deploying a newly developed compact diode-pumped solid state (DPSS) laser with emission at 315 nm. The laser is based on the quasi-three-level transition in Nd:YAG at 946 nm. The pulsed operation is either realized by an active Q-switch using an electro-optical device or by introduction of a Cr<SUP>4+</SUP>:YAG saturable absorber as passive Q-switch element. By extra-cavity second harmonic generation in different nonlinear crystal media we obtained blue light at 473 nm. Subsequent mixing of the fundamental and the second harmonic in a β-barium-borate crystal provided pulsed emission at 315 nm with up to 20 μJ maximum pulse energy and 17 ns pulse duration. Substitution of a nitrogen laser in a FIA diagnostics system by the DPSS laser succeeded in considerable improvement of the detection limit. Despite significantly lower pulse energies (7 μJ DPSS laser versus 150 μJ nitrogen laser), in preliminary investigations the limit of detection was reduced by a factor of three for a typical FIA.
Two examples of our biophotonic research utilizing nanoparticles are presented, namely laser-based fluoroimmuno analysis and in-vivo optical oxygen monitoring. Results of the work include significantly enhanced sensitivity of a homogeneous fluorescence immunoassay and markedly improved spatial resolution of oxygen gradients in root nodules of a legume species.
In this paper, we consider families of time Markov fields (or reciprocal classes) which have the same bridges as a Brownian diffusion. We characterize each class as the set of solutions of an integration by parts formula on the space of continuous paths C[0; 1]; R-d) Our techniques provide a characterization of gradient diffusions by a duality formula and, in case of reversibility, a generalization of a result of Kolmogorov.
We develop a cluster expansion in space-time for an infinite-dimensional system of interacting diffusions where the drift term of each diffusion depends on the whole past of the trajectory; these interacting diffusions arise when considering the Langevin dynamics of a ferromagnetic system submitted to a disordered external magnetic field.
The authors analyse different Gibbsian properties of interactive Brownian diffusions X indexed by the d-dimensional lattice. In the first part of the paper, these processes are characterized as Gibbs states on path spaces. In the second part of the paper, they study the Gibbsian character on R^{Z^d} of the law at time t of the infinite-dimensional diffusion X(t), when the initial law is Gibbsian. AMS Classifications: 60G15 , 60G60 , 60H10 , 60J60
We prove in this paper an existence result for infinite-dimensional stationary interactive Brownian diffusions. The interaction is supposed to be small in the norm ||.||∞ but otherwise is very general, being possibly non-regular and non-Markovian. Our method consists in using the characterization of such diffusions as space-time Gibbs fields so that we construct them by space-time cluster expansions in the small coupling parameter.