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It is shown that several polymers can form insoluble interfacial layers on a poly (ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) layer after annealing of the double-layer structure. The thickness of the interlayer is dependent on the characteristics of the underlying PEDOT.PSS and the molecular weight of the polymers. It is further shown that the electronic structures of the interlayer polymers have a significant effect on the properties of red-light-emitting polymer-based electrophosphorescent devices. Upon increasing the highest occupied molecular orbital and lowest unoccupied molecular orbital positions, a significant increase in current density and device efficiency is observed. This is attributed to efficient blocking of electrons in combination with direct injection of holes from the interlayer to the phosphorescent dye. Upon proper choice of the interlayer polymer, efficient red, polymer-based electrophosphorescent devices with a peak luminance efficiency of 5.5 cd A(-1) (external quantum efficiency = 6 %) and a maximum power-conversion efficiency of 5 Im W-1 can be realized.
We investigated the spectral properties of light-emitting diodes based on a deep blue-emitting pyrazoloquinoline dye doped into a poly(N-vinylcarbazole)-based matrix. Even though the electroluminescence (EL) of the host is redshifted and broadened with respect to the emission of the dye, the EL spectrum becomes fully dominated by the dye emission at concentrations of ca. 2 wt %. This is attributed to a competition of exciplex formation on the matrix and exciton formation on the dye.
We report that the performances of blue polymer electrophosphorescent devices are crucially depending on the choice of the electron transporting material incorporated into the emissive layer. Devices with 1,3-bis[(4-tert- butylphenyl)-1,3,4-oxidiazolyl]phenylene (OXD-7) doped at similar to 40 wt% into a poly(vinylcarbazole) matrix exhibited significantly higher efficiencies than those with 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), yielding maximum luminous and power efficiency values of 18.2 Cd/A and 8.8 lm/W, respectively. Time resolved photoluminescence measurements revealed a long lifetime phosphorescence component in layers with PBD, which we assign to significant triplet harvesting by this electron-transporting component. (c) 2006 American Institute of Physics
Translational diffusion of fluorescent tracer molecules in azobenzene polymer layers is studied at different temperatures and under illumination using the method of fluorescence recovery after photobleaching. Diffusion is clearly observed in the dark above the glass transition temperature, while homogeneous illumination at 488 nm and 100 mW/cm(2) does not cause any detectable diffusion of the dye molecules within azobenzene layers. This implies that the viscosity of azobenzene layers remains nearly unchanged under illumination with visible light in the absence of internal or external forces. (c) 2006 American Institute of Physics.
In most stochastic models addressing the persistence of small populations, environmental noise is included by imposing a synchronized effect of the environment on all individuals. However, buffer mechanisms are likely to exist that may counteract this synchronization to some degree. We have studied whether the flexibility in the mating system, which has been observed in some bird species, is a potential mechanism counteracting the synchronization of environmental fluctuations. Our study organism is the lesser spotted woodpecker Picoides minor (Linnaeus), a generally monogamous species. However, facultative polyandry, where one female mates with two males with separate nests, was observed in years with male-biased sex ratio. We constructed an individual-based model from data and observations of a population in Taunus, Germany. We tested the impact of three behavioural scenarios on population persistence: (1) strict monogamy; (2) polyandry without costs; and (3) polyandry assuming costs in terms of lower survival and reproductive success for secondary males. We assumed that polyandry occurs only in years with male-biased sex ratio and only for females with favourable breeding conditions. Even low rates of polyandry had a strong positive effect on population persistence. The increase of persistence with carrying capacity was slower in the monogamous scenario, indicating strong environmental noise. In the polyandrous scenarios, the increase of persistence was stronger, indicating a buffer mechanism. In the polyandrous scenarios, populations had a higher mean population size, a lower variation in number of individuals, and recovered faster after a population breakdown. Presuming a realistic polyandry rate and costs for polyandry, there was still a strong effect of polyandry on persistence. The results show that polyandry and in general flexibility in mating systems is a buffer mechanism that can significantly reduce the impact of environmental and demographic noise in small populations. Consequently, we suggest that even behaviour that seems to be exceptional should be considered explicitly when predicting the persistence of populations
The trans diesters of 1,4-cyclohexanediol with a number of acetic acid analogues, CX3COOH, of varying steric hindrance and polarity (CX3 = Me, Et, iso-Pr, tert-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, CBr3) were synthesized, and the axial, axial/equatorial, equatorial conformational equilibria were studied by low-temperature H-1 NMR spectroscopy in CD2Cl2. The structures and relative energies of the axial, axial and equatorial, equatorial conformers were calculated at both the MP2/6-311G* and the MP2/6-311+G* levels of theory, and it was only by including diffuse functions that a good correlation of Delta G degrees(calcd) vs Delta G(exptl) could be obtained. Both the structures and the energy differences of the axial, axial and equatorial, equatorial conformers are discussed with respect to the established models of conformational analysis, viz., steric 1,3-diaxial and hyperconjugative interactions. Interestingly, the hyperconjugative interactions sigma(C-C)/sigma(C-H)->sigma*(C-O), together with a steric effect which also destabilizes the equatorial, equatorial conformers on increasing bulk of the substituents, proved to dominate the position of the conformational equilibria. In addition, the preference of the axial, axial conformers with respect to their equatorial, equatorial analogues was greater than expected from the conformational energies of the corresponding substituents in the monosubstituted cyclohexyl esters. The reason for this very interesting and unexpected result is also discussed
The regioselectivities of methyl- and phenylhydrazine with acridin-9-yl isothiocyanate (thus yielding thiosemicarbazides with acridine substituted on the urea-type side) were examined. Methythydrazine regioselectivity was high with the alpha-nitrogen atom overwhelmingly more nucleophilic than the beta-nitrogen atom; phenylhydrazine regioselectivity was poor but varied with the solvent and only in the case of ethanol was nucleophilic predominance of the alpha-nitrogen atom pronounced. Of note, whilst both phenyl thiosemicarbazides were present in solution only as spiro forms, the methyl product was present as an equilibrium mixture of open-chain and spiro thiosemicarbazides. Reactions on the NH2 blocked analogue of methyl acridin-9-ylthiosemicarbazide (1-isopropylidene-2- methylthiosemicarbazide) were also examined. Interestingly, present in the starting material itself was a structural motif of novelty wherein a triazolethione represented the major species of an equilibrium between cyclic and open-chain forms
Different chemical and enzymatic methods were applied for the hydrolysis of main stems from Lupinus nootkatensis (harvest November 2002). The whole process (all steps) is based on the lignocellulose-feedstock biorefinery regime. The acid hydrolysis of L. was performed with concentrated hydrochloric acid; advantages in this process are exothermic hydrolysis and the possibility of acid recovery. Enzymatic hydrolysis achieved high yields of fermentable carbohydrates (regarding to input cellulose) with high selectivity. However, this way requires the generation of cellulose from L. by chemical pulping. Monosaccharide derivatives thus obtained were identified by their GC retention times and the corresponding MS fragmentation. Hexamethyldisilazane was used as derivatization reagent to prepare the trimethylsilyl derivatives of the carbohydrates and of the degradations products of cellulose from the different fractions. The glucose content was quantified by GC peak integration with respect to an internal standard.
The new tetrathiacrown ethers maleonitrile-tetrathia-12-crown-4 (mn12S(4)) and maleonitrile-tetrathia-13-crown- 4 (mn13S(4)) have been prepared and characterised by X-ray crystallographic analysis. These crown ethers form 2:1, 3:2 and 1: 1 complexes with AgY (Y = BF4, PF6). The crystal structures of [Ag(mn12S(4))(2)]BF4 (3a), [Ag(mn13S(4))(2)]BF4 (4a) and [Ag-2(mn13S(4))(3)](PF6)(2) (6b) have been determined. Compound 3a contains the centrosymmetric sandwich complex cation [Ag(mn12S(4))(2)](+) where each mn12S(4) ligand is coordinated to the Ag centre in an endo manner through all four S atoms. The 2:1 complex [Ag(mn12S(4))(2)](+) is the first sandwich complex with a tetrathiacrown ether and the first complex with an octa(thioether) coordination sphere. The crystal structure of compound 4a also reveals a 2:1 complex. This complex, [Ag(mnl3S(4))(2)](+), exhibits a half-sandwich structure. One mn13S(4) ligand coordinates to Ag+ by all four S donor atoms and the other 13S(4) crown by only one S atom. Compound 6b contains a dinuclear Ag complex. The Ag complexes 3a,b-8a,b were also studied by electrospray ionisation mass spectrometry. Collision-induced dissociation (CID) was used to compare the relative stability of 2:1 complexes [AgL2]+ and 1:1 complexes [AgL](+) (L = mn12S(4), mn13S(4)). The C-13 NMR chemical shifts of 2:1 and 1:1 Ag complexes and their corresponding free ligands were also estimated and compared. The free energy of the barrier of ring inversion (Delta G(double dagger)) for [Ag(mn12S(4))(2)](+) was determined to be 64 kJmol(-1).
Electrospray ionization was employed to study the mass spectrometric behavior of the maleonitrile tetrathiacrown ethers mn12S(4) (1) and mn13S(4) (2) and maleonitrile pentathiacrown ether mn15S(5) (3) and of their complexes with various metal salts (MX2, M=Pd, Pt, Ni, Co, Fe; X=Cl, CrCl3, Ni(BF4)(2), TIPF6 or Cd(NO3)(2)) and Cu(SO3CF3)(2). Both singly charged, [MXL](+) and [MXL2]+, and doubly charged complexes, [MLn](2+) (n = 2-5), were observed. The formation of the different complexes consisting of the transition metal ion, the counterion and the various crown ethers and their subsequent dissociation was also studied by collision-induced dissociation measurements which were also used to evaluate the relative stabilities of the complexes. It was found that the collisional voltages for the dissociation of the complexes were generally greater in the [MXL](+) complexes than in the corresponding [MXL2]+ complexes. Copyright (c) 2006 John Wiley & Sons, Ltd
A new functional group, the hydroxy group, was inserted into a Betti base by reaction with salicylaldehyde, and the naphthoxazine derivatives thus obtained were converted by ring-closure reactions with formaldehyde, acetaldehyde, propionaldehyde or phosgene to the corresponding naphth[1',2':5,6][1,3]oxazino[3,2-c][1,3]benzoxazine derivatives. Further, the conformational analysis of these polycyclic compounds by NMR spectroscopy and an accompanying molecular modelling are reported; especially, both quantitative anisotropic ring current effects of the aromatic moieties in these compounds and steric substituent effects were employed to determine the stereochemistry of the naphthoxazinobenzoxazine derivatives.
Variously substituted tolanes were employed to show that the push-pull effect is also active in C equivalent to C triple bonds by the successful correlation of the occupation quotient pi*/pi of the pi orbital in resonance with the substituted phenyl moieties of tolanes versus the bond length of the C equivalent to C triple bond. In addition, the influences of the ortho phenyl ring substituents on the C-13 chemical shifts of the triple bond carbon atoms, which were estimated by Rubin et al.(4) to be "inapplicable for describing triple bond polarization", were re-evaluated, leading to the conclusion that, while anisotropic effects of ortho substituents are negligible, the steric ortho-substituent effects do in fact dominate the deviations obtained. A detailed theoretical NBO/NCS study has been employed to illuminate the facts of this case
Push-pull alkenes are substituted alkenes with one or two electron-donating substituents on one end of C=C double bond and with one or two electron-accepting substituents at the other end. Allowance for pi-electron delocalization leads to the central C=C double bond becoming ever more polarized and with rising push-pull character, the pi-bond order of this double bond is reduced and, conversely, the corresponding pi-bond orders of the C-Don and C- Ace bonds are accordingly increased. This push-pull effect is of decisive influence on both the dynamic behavior and the chemical reactivity of this class of compounds and thus it is Of Considerable interest to both determine and to quantify the inherent push-pull effect. previously, the barriers to rotation about the C=C, C-Don and/or C-Acc partial double bonds (Delta G(not equal), as determined by dynamic NMR spectroscopy) or the C-13 chemical shift difference of the polarized C=C partial double bond (Delta delta(C=C)) were employed for this purpose, However, these parameters can have serious limitations, viz. the barriers can be immeasurable on the NMR timescale (either by being too high or too low-, heavily-biased conformers are present, etc.) or Delta delta(C=C) behaves in a non-additive manner with respect to the combination of the four substituents. Hence, a general parameter to quantify the push-pull effect is not yet available. Ab initio MO calculations on a collection of compounds, together with NBO analysis, provided valuable information on the structure, bond energies, electron occupancies and bonding/antibonding interactions. In addition to Delta G(C=C)(not equal) (either experimentally determined or theoretically calculated) and Delta delta(C=C), the bond length of the C=C partial double bond was also examined and it proved to be a reliable parameter to quantify the push-pull effect. Equally so, the quotient of the occupation numbers of the antibonding and bonding pi orbitals of the central C=C partial double bond ( pi*(C=C)/pi(C=C) ) could also be employed for this purpose
The reaction of methyl acridin-9-ylthiosemicarbazide under basic conditions with methyl bromoacetate resulted in a 1,3-thiazolin-4-one structure as provided by X-ray crystallography. The structure forced a re-evaluation of the reactant methyl acridin-9-ylthiosemicarbazide, originally thought to be 2-methyl 4-acridin-9-ylthiosemicarbazide based on synthetic expectations, but which when examined by X-ray crystallography was found to be in fact the isomeric 2- methyl 1-acridin-9-ylthiosemicarbazide resulting from rearrangement via a spiro form which it is in equilibrium with in solution. The product resulting from reaction with methyl iodide was also studied and the previously reported semicarbazide produced by reaction with MNO was re-examined. In both cases, the 1,2 isomer rather than the 2,4 isomer was found to be present based on the sign of the 3JCH3,N11 coupling. Full characterization of the compounds was rendered by 1H, 13C, and 15N solution-state NMR, and in the solid state, by both 13C and 15N NMR.
Dynamic NMR of 1-(methylsulfonyl)-3,5-bis(trifluoromethylsulfonyl)-1,3,5-triazinane reveals the existence of three conformers and two dynamic processes: ring inversion and rotation about the N-S bond, both processes having Delta G(double dagger) = 13.5 kcal/mol. An unprecedented large reverse Perlin effect (J(CHax) > J(CHeq)) was found experimentally and calculated theoretically.
A successful assignment for the fundamental bands observed in the experimental IR spectra of mn-12S(2)O(2) and fn-12S(2)O(2) dithiacrown ethers was achieved by the aid of the density functional theory (DFT) based quantum mechanical calculations carried out at the 133LYP/6-31G(d) and B3LYP/6-31 + G(d) level of theory. Two different scaling approaches, '(i) scaled quantum mechanics force field (SQM FF) methodology', and (ii) the 'scaling frequencies with dual empirical scale factors', were used in order to fit the calculated harmonic frequencies to the experimental ones. Potential energy distribution (PED) calculations were carried out to define the internal coordinate contributions to each normal mode and to define the corresponding normal modes of the molecules. The effects of the conformational differences onto the IR active normal modes of the two isomeric molecules and their corresponding experimental frequencies were discussed in the light of the calculated spectral data.
Both the structure and intramolecular flexibility of a series of aza crown ethers were studied by experimental NMR and theoretical molecular modeling. The stoichiometries of complexation to the anions H2PO4- and resulting complex stabilities were determined by experimental NMR (1H, 31P) titration and, in addition, the structure and mobility changes of the aza crown ethers upon complexation were also examined.
The paper is focused on the characterization and use of phosphatidylcholine (PC)-based inverse microemulsions as a template phase for the CdS nanoparticle formation. The optically clear, isotropic phase in the oil corner was identified as a "classicalö water-in-oil microemulsion by means of NMR-diffusion measurements. Because of the very small dimensions of the water droplets, the isotropic phase shows a Newtonian-like flow behavior, and adequate amounts of bulk water cannot be detected by DSC. It is demonstrated that this w/o microemulsion can be used successfully as a nanoreactor for the formation of CdS nanoparticles with diameters of 4-5 nm. During the following process of solvent evaporation the individual small CdS nanoparticles aggregate to significant larger cubic nanoparticles, with an edge length of 2-40 nm, arranged in well-defined mosaic-like superstructures. In presence of SDS the nanocubes were stable up to 800 °C. It has to be stated here that polyelectrolytes prevent the formation of such well-ordered superstructures.
We present an approach to generate (multivariate) twin surrogates (TS) based on recurrence properties. This technique generates surrogates which correspond to an independent copy of the underlying system, i.e. they induce a trajectory of the underlying system starting at different initial conditions. We show that these surrogates are well suited to test for complex synchronisation and exemplify this for the paradigmatic system of Rossler oscillators. The proposed test enables to assess the statistical relevance of a synchronisation analysis from passive experiments which are typical in natural systems
When the eyes fixate at a point in a visual scene, small saccades rapidly shift the image on the retina. The effect of these microsaccades on the latency of subsequent large-scale saccades may be twofold. First, microsaccades are associated with an enhancement of visual perception. Their occurrence during saccade target perception should, thus, decrease saccade latencies. On the other hand, microsaccades likely indicate activity in fixation-related oculomotor neurons. These represent competitors to saccade-related cells in the interplay of gaze holding and shifting. Consequently, an increase in saccade latencies after microsaccades would be expected. Here, we present evidence for both aspects of microsaccadic impact on saccade latency. In a delayed response task, participants made saccades to visible or memorized targets. First, microsaccade occurrence up to 50 ms before target disappearance correlated with 18 ms (or 8%) faster saccades to memorized targets. Second, if microsaccades occurred shortly (i.e., < 150 ms) before a saccade was required, saccadic reaction times in visual and memory trials were increased by about 40 ms (or 16%). Hence, microsaccades can have opposite consequences for saccade latencies, pointing at a differential role of these fixational eye movements in preparation of motor programs.
A 13.94-m-long sediment core, collected from a medium-sized lake in the Qilian Mountains (NE Tibetan Plateau, China), was analysed palynologically at 81 horizons. The interpretation of indicator taxa yielded various vertical shifts of the vegetation belts. These palaeovegetation results have been checked with lake surface pollen spectra from 8 takes representing different altitudinal vegetation belts. Our main findings are the following: A short period of the late Marine Isotope Stage 3 (around similar to 46,000 yr ago) was characterized by interglacial temperature conditions with a tree line above its present-day altitude. During the LGM, the vicinity of the lake was not covered by ice but by sparse alpine vegetation and alpine deserts, indicating that the climate was colder by similar to 4-7 degrees C than today Markedly higher temperatures were inferred from higher arboreal pollen frequencies between similar to 13,000 and similar to 7000 yr ago with a Holocene temperature optimum and a maximal Picea-Betula mixed-forest expansion between similar to 9000 and similar to 7000 yr ago, when temperatures exceeded the present-day conditions by at least 1-2 degrees C. Alpine steppes and meadows and sub-alpine shrub vegetation dominated around the lake since the middle Holocene, suggesting that vegetation and climate conditions were exceptionally stable in comparison to previous periods.
The late-Quaternary climate history of monsoonal Central Asia was inferred from 75 palaeoclimatic records which provide information about moisture conditions in the last 50 ka (or part of this period). Wet conditions occurred during middle and late Marine Isotope Stage 3, while the Last Glacial Maximum (LGM) was characterized by dry climate conditions in the region. A stepwise climate amelioration is suggested by the climate records following the LGM. Several climate signals of this period, which were reported from high-latitude ice core records, are preserved in archives from monsoonal Central Asia as well. During the early Holocene, high effective moisture was inferred from most records from the area dominated by the Indian Monsoon (e.g. the Tibetan Plateau) suggesting that Holocene optimal climate conditions occurred there during this period. In contrast, areas which are dominated by the South-East Asian monsoon (SE Monsoon) and the Westerlies (in north-western and north-central China, Mongolia) do not uniformly show an early Holocene climate optimum. For this area optimal conditions prevailed during the mid-Holocene. These apparent contradictions can possibly be explained by the regional uplift and descent of air masses in the Holocene. During the early Holocene, strengthened insolation possibly caused an enhanced low-level convergence over the Tibetan Plateau which led to the intensification of the summer monsoon. The strong air uplift caused intensified precipitation and air divergence in the upper troposphere over the Tibetan Plateau. The areas adjacent to the north therefore experienced an intensified descent of air masses and consequently increased aridity. The majority of the palaeoclimatic records suggest reduced effective moisture since the late Holocene in the region.
Recent and subfossil pollen spectra from the Alashan Plateau are presented in order to provide information on desert plant representation and on recent changes in vegetation and climate in this remote area in northern China. The desert vegetation composition is faithfully represented by the surface pollen spectra. The comparison of the desert plant species to the related pollen taxa yielded the following sequence from over-representation to under- representation: Chenopodiaceae, Artemisia, Ephedra fragilis-type s.l., Reaumuria, Nitraria and Calligonum. A 72 cm long sediment record from a small hydrologically-closed inter-dune lake (SE Badan Jilin Sand Sea, southern Alashan Plateau) covering the past similar to 160 years (dated by(137)Cs) was analysed palynologically. Intervals of denser Artemisia coverage on the sand dunes around the lake, indicating wetter climate, occurred from the mid-1850s to the mid-1870s, during the first two decades of the 20th century and from the late 1930s to the beginning of the 1960s
Reading requires the orchestration of visual, attentional, language-related, and oculomotor processing constraints. This study replicates previous effects of frequency, predictability, and length of fixated words on fixation durations in natural reading and demonstrates new effects of these variables related to previous and next words. Results are based on fixation durations recorded from 222 persons, each reading 144 sentences. Such evidence for distributed processing of words across fixation durations challenges psycholinguistic immediacy-of-processing and eye-mind assumptions. Most of the time the mind processes several words in parallel at different perceptual and cognitive levels. Eye movements can help to unravel these processes.
Background: Racing drivers require multifaceted cognitive and physical abilities in a multitasking situation. A knowledge of their physical capacities may help to improve fitness and performance. Objective: To compare reaction time, stability performance capacity, and strength performance capacity of elite racing drivers with those of age-matched, physically active controls. Methods: Eight elite racing drivers and 10 physically active controls matched for age and weight were tested in a reaction and determination test requiring upper and lower extremity responses to visual and audio cues. Further tests comprised evaluation of one-leg postural stability on a two-dimensional moveable platform, measures of maximum strength performance capacity of the extensors of the leg on a leg press, and a test of force capacity of the arms in a sitting position at a steering wheel. An additional arm endurance test consisted of isometric work at the steering wheel at + 30 degrees and -30 degrees where an eccentric threshold load of 30 N.m was applied. Subjects had to hold the end positions above this threshold until exhaustion. Univariate one way analysis of variance (alpha = 0.05) including a Bonferroni adjustment was used to detect group differences between the drivers and controls. Results: The reaction time of the racing drivers was significantly faster than the controls ( p = 0.004). The following motor reaction time and reaction times in the multiple determination test did not differ between the groups. No significant differences (p> 0.05) were found for postural stability, leg extensor strength, or arm strength and endurance. Conclusions: Racing drivers have faster reaction times than age-matched physically active controls. Further development of motor sport-specific test protocols is suggested. According to the requirements of motor racing, strength and sensorimotor performance capacity can potentially be improved.
In this paper we present an approach to recover the dynamics from recurrences of a system and then generate (multivariate) twin surrogate (TS) trajectories. In contrast to other approaches, such as the linear-like surrogates, this technique produces surrogates which correspond to an independent copy of the underlying system, i. e. they induce a trajectory of the underlying system visiting the attractor in a different way. We show that these surrogates are well suited to test for complex synchronization, which makes it possible to systematically assess the reliability of synchronization analyses. We then apply the TS to study binocular fixational movements and find strong indications that the fixational movements of the left and right eye are phase synchronized. This result indicates that there might be one centre only in the brain that produces the fixational movements in both eyes or a close link between two centres.
When top sports performers fail or “choke” under pressure, everyone asks: why? Research has identified a number of conditions (e.g. an audience) that elicit choking and that moderate (e.g. trait-anxiety) pressure – performance relation. Furthermore, mediating processes have been investigated. For example, explicit monitoring theories link performance failure under psychological stress to an increase in attention paid to a skill and its step-by-step execution (Beilock & Carr, 2001). Many studies have provided support for these ideas. However, so far only overt performance measures have been investigated which do not allow more thorough analyses of processes or performance strategies. But also a theoretical framework has been missing, that could (a) explain the effects of explicit monitoring on skill execution and that (b) makes predictions as to what is being monitored during execution. Consequently in this study, the nodalpoint hypothesis of motor control (Hossner & Ehrlenspiel, 2006) was taken to predict movement changes on three levels of analysis at certain “nodalpoints” within the movement sequence. Performance in two different laboratory tasks was assessed with respect to overt performance (the observable result, for example accuracy in the target), covert performance (description of movement execution, for example the acceleration of body segements) and task exploitation (the utilization of task properties such as covariation). A fake competition (see Beilock & Carr, 2002) was used to invoke pressure. In study 1 a ball bouncing task in a virtual-reality set-up was chosen. Previous studies (de Rugy, Wei, Müller, & Sternad, 2003) have shown that learners are usually able to “passively” exploit the dynamical stability of the system. According to explicit monitoring theories, choking should be expected either if the task itself evokes an “active control” (Experiment 1) or if learners are provided with explicit instructions (Experiment 2). In both experiments, participants first went through a practice phase on day 1. On day 2, following the Baseline Test participants were divided into a High-Stress or No-Stress Group for the final Performance Test. The High-Stress Group entered a fake competition. Overt performance was measured by the Absolute Error (AE) of ball amplitudes from target height; covert performance was measured by Period Modulation between successive hits and task exploitation was measured by Acceleration (AC) at ball-racket impact and Covariation (COV) of impact parameters. To evoke active control in Exp. 1 (N=20), perturbations to the ball flight were introduced. In Exp. 2 (N=39) half of the participants received explicit skill-focused instructions during learning. For overt performance, results generally show an interaction between Stress Group and Test, with better performance (i. e. lower AE) for the High-Stress group in the final Performance Test. This effect is also independent of the Instructions that participants had received during learning (Exp. 2). Similar effects were found for COV but not for AC. In study 2 a visuomotor tracking task in which participants had to pursuit a target cross that was moving on an invisible curve. This curve consisted of 3 segments of 6 turning points sequentially ordered around the x-axis. Participants learned two short movement sequences which were then concatenated to form a single sequence. It was expected that under pressure, this sequence should “fall apart” at the point of concatenation. Overt Performance was assessed by the Root Mean Square Error between target and pursuit cross as well as the Absolute Error at the turning points, covert performance was measured by the Latency from target to pursuit turning and task exploitation was measured by the temporal covariation between successive intervals between turning points. Experiment 3 (intraindividual variation) as well as Experiment 4 (interindividual variation) show performance enhancement in the pressure situation on the overt level with matching results on covert and task exploitation level. Thus, contrary to previous studies, no choking under pressure was found in any of the experiments. This may be interpreted as a failure in the experimental manipulation. But certainly also important characteristics of the task are highlighted. Choking should occur in tasks where performers do not have the time to use action or thought control strategies, that are more relevant to their “self” and that are discrete in nature.
The limited capacity of working memory forces people to update its contents continuously. Two aspects of the updating process were investigated in the present experimental series. The first series concerned the question if it is possible to update several representations in parallel. Similar results were obtained for the updating of object features as well as for the updating of whole objects, participants were able to update representations in parallel. The second experimental series addressed the question if working memory representations which were replaced in an updating disappear directly or interfere with the new representations. Evidence for the existence of old representations was found under working memory conditions and under conditions exceeding working memory capacity. These results contradict the hypothesis that working memory contents are protected from proactive interference of long-term memory contents.
Interdisziplinäres Zentrum für Musterdynamik und Angewandte Fernerkundung Workshop vom 9. - 10. Februar 2006
Inversions of an individual geophysical data set can be highly nonunique, and it is generally difficult to determine petrophysical parameters from geophysical data. We show that both issues can be addressed by adopting a statistical multiparameter approach that requires the acquisition, processing, and separate inversion of two or more types of geophysical data. To combine information contained in the physical-property models that result from inverting the individual data sets and to estimate the spatial distribution of petrophysical parameters in regions where they are known at only a few locations. we demonstrate the potential of the fuzzy c-means (FCM) clustering technique. After testing this new approach on synthetic data, we apply it to limited crosshole georadar, crosshole seismic, gamma-log, and slug-test data acquired within a shallow alluvial aquifer. The derived multiparameter model effectively outlines the major sedimentary units observed in numerous boreholes and provides plausible estimates for the spatial distributions of gamma-ray emitters and hydraulic conductivity
In an attempt to map the shallow geometry of the Maleme Fault Zone (North Island, New Zealand) and estimate vertical displacements of selected fault strands, we have collected 2D and 3D georadar data using 100 MHz antennae. The 2D data consisted of three parallel georadar lines recorded perpendicular to the axis of the well-defined graben of the Maleme Fault Zone. These similar to 160 in long lines, which were 7.5 m apart, crossed several fault strands on either side of the graben axis. The processed georadar sections revealed two prominent parallel reflections that originated from the boundaries of Late Pleistocene lacustrine and tephra deposits. Distinct vertical offsets of these reflections allowed us to estimate displacernents at individual fault strands across the entire inner graben. The total displacements represented by these offsets was similar to 10-20% greater than that inferred from geomorphological studies, thus demonstrating the limitations of surface observations for determining cumulative fault movements. The 3D georadar data set, recorded across an area of similar to 70x similar to 20 in to one side of the graben axis, provided key details on individual fault strands. For the 3D visualization of fault-related structures, various spatial attribute analyses based on the cosine of the instantaneous phase proved to be useful
The vertical radar profiling (VRP) technique uses surface-to-borehole acquisition geometries comparable to vertical seismic profiling (VSP). Major differences between the two methods do arise due to the fundamentally differing nature of the velocity-depth gradients and transmitter/receiver directivities. Largely for this reason, VRP studies have so far essentially been limited to the reconstruction of velocity-depth profiles by inverting direct arrival times from single-offset VRP surveys. In this study, we investigate the potential to produce high-resolution subsurface reflection images from multi-offset VRP data. Two synthetic data sets are used to evaluate a processing strategy suitably adapted from VSP processing. Despite the fundamental differences between VRP and VSP data, we found that our processing approach is capable of reconstructing subsurface structures of comparable complexity to those routinely imaged by VSP data. Finally, we apply our processing flow to two multi-offset VRP data sets recorded at a well constrained hydrogeophysical test site in SW-Germany. The inferred VRP images are compared with high-quality surface georadar reflection images and lithological logs available at the borehole locations. We find that the VRP images are in good agreement with the surface georadar data and reliably detect the major lithological boundaries. Due to the significantly shorter ray-paths, the depth penetration of the VRP data is, however, considerably higher than that of the surface georadar data. VRP reflection images thus provide an effective means for the depth-calibration and extension of conventional surface georadar data in the vicinity of boreholes.
Current advances in SWIFT
(2006)
Models of eye movement control are very useful for gaining insights into the intricate connections of different cognitive and oculomotor subsystems involved in reading. The SWIFT model (Engbert, Longtin, & Kliegl (2002). Vision Research, 42, 621 - 636) proposed a unified mechanism to account for all types of eye movement patterns that might be observed in reading behavior. The model is based on the notion of spatially distributed, or parallel, processing of words in a sentence. We present a refined version of SWIFT introducing a letter-based approach that proposes a processing gradient in the shape of a smooth function. We show that SWIFT extents its capabilities by accounting for distributions of landing positions.
Reading requires the orchestration of visual, attentional, language-related, and oculomotor processing constraints. This study replicates previous effects of frequency, predictability, and length of fixated words on fixation durations in natural reading and demonstrates new effects of these variables related to previous and next words. Results are based on fixation durations recorded from 222 persons, each reading 144 sentences. Such evidence for distributed processing of words across fixation durations challenges psycholinguistic immediacy-of-processing and eye- mind assumptions. Most of the time the mind processes several words in parallel at different perceptual and cognitive levels. Eye movements can help to unravel these processes
When the eyes fixate at a point in a visual scene, small saccades rapidly shift the image on the retina. The effect of these microsaccades on the latency of subsequent large-scale saccades may be twofold. First, microsaccades are associated with an enhancement of visual perception. Their occurrence during saccade target perception could, thus, decrease saccade latencies. Second, microsaccades are likely to indicate activity in fixation-related oculomotor neurons. These represent competitors to saccade-related cells in the interplay of gaze holding and shifting. Consequently, an increase in saccade latencies would be expected after microsaccades. Here, we present evidence for both aspects of microsaccadic impact on saccade latency. In a delayed response task, participants made saccades to visible or memorized targets. First, microsaccade occurrence up to 50 ms before target disappearance correlated with 18 ms (or 8%) faster saccades to memorized targets. Second, if microsaccades occurred shortly (i.e., < 150 ms) before a saccade was required, mean saccadic reaction time in visual and memory trials was increased by about 40 ms (or 16%). Hence, microsaccades can have opposite consequences for saccade latencies, pointing at a differential role of these fixational eye movements in the preparation of saccade motor programs
Effects of frequency, predictability, and position of words on event-related potentials were assessed during word-by-word sentence reading in 48 subjects in an early and in a late time window corresponding to P200 and N400. Repeated measures multiple regression analyses revealed a P200 effect in the high-frequency range also the P200 was larger on words at the beginning and end of sentences than on words in the middle of sentences (i.e., a quadratic effect of word position). Predictability strongly affected the N400 component; the effect was stronger for low than for high- frequency words. The P200 frequency effect indicates that high-frequency words are lexically accessed very fast, independent of context information. Effects on the N400 suggest that predictability strongly moderates the late access especially of low-frequency words. Thus, contextual facilitation on the N400 appears to reflect both lexical and post- lexical stages of word recognition, questioning a strict classification into lexical and post-lexical processes.
Previous research has shown that in a three-term spatial reasoning task, the second premise of a German premise pair is especially easy to comprehend if (1) the prepositional object rather than the grammatical subject denotes the given entity, and if (2) the term denoting the given entity precedes the term denoting the new entity. Accordingly, the second premise is easiest to comprehend with noncanonical word order-that is, with the prepositional object in preverbal position denoting the given entity (e.g., To the right of the given object is the new subject). This finding is explained in terms of contextual licensing of noncanonical word order. Here, we discuss and tested two alternative accounts of contextual licensing, given-new and partially ordered set relations (Poset). The given-new account claims that noncanonical word order is licensed by the term denoting the given entity preceding the term denoting the new entity. On the Poset account, noncanonical word order is licensed if the preverbal constituent introduces a new entity that stands in a transitive, irreflexive, and asymmetric relation to a given entity. Comprehension times for second premises with spatial adverbs in four different word orders support both accounts of contextual licensing; Poset licensing was stronger than given-new licensing.
A mathematical model of working-memory capacity limits is proposed on the key assumption of mutual interference between items in working memory. Interference is assumed to arise from overwriting of features shared by these items. The model was fit to time-accuracy data of memory-updating tasks from four experiments using nonlinear mixed effect (NLME) models as a framework. The model gave a good account of the data from a numerical and a spatial task version. The performance pattern in a combination of numerical and spatial updating could be explained by variations in the interference parameter: assuming less feature overlap between contents from different domains than between contents from the same domain, the model can account for double dissociations of content domains in dual-task experiments. Experiment 3 extended this idea to similarity within the verbal domain. The decline of memory accuracy with increasing memory load was steeper with phonologically similar than with dissimilar material, although processing speed was faster for the similar material. The model captured the similarity effects with a higher estimated interference parameter for the similar than for the dissimilar condition. The results are difficult to explain with alternative models, in particular models incorporating time-based decay and models assuming limited resource pools.