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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
Triplet energy back transfer in conjugated polymers with pendant phosphorescent iridium complexes
(2006)
The nature of Dexter triplet energy transfer between bonded systems of a red phosphorescent iridium complex 13 and a conjugated polymer, polyfluorene, has been investigated in electrophosphorescent organic light-emitting diodes. Red- emitting phosphorescent iridium complexes based on the [Ir(btp)2(acac)]fragment (where btp is 2-(2 '- benzo[b]thienyl)pyridinato and acac is acetylacetonate) have been attached either directly (spacerless) or through a - (CH2)(8)-chain (octamethylene-tethered) at the 9-position of a 9-octylfluorene host. The resulting dibromo- functionalized spacerless (8) or octamethylene-tethered (12) fluorene monomers were chain extended by Suzuki polycondensations using the bis(boronate)-terminated fluorene macromonomers 16 in the presence of end-capping chlorobenzene solvent to produce the statistical spacerless (17) and octamethylene-tethered ( 18) copolymers containing an even dispersion of the pendant phosphorescent fragments. The spacerless monomer 12 adopts a face-to-face conformation with a separation of only 3.6 angstrom between the iridium complex and fluorenyl group, as shown by X-ray analysis of a single crystal, and this facilitates intramolecular triplet energy transfer in the spacerless copolymers 17. The photo- and electroluminescence efficiencies of the octamethylene-tethered copolymers 18 are double those of the spacerless copolymers 17, and this is consistent with suppression of the back transfer of triplets from the red phosphorescent iridium complex to the polyfluorene backbone in 18. The incorporation of a -(CH2)(8)- chain between the polymer host and phosphorescent guest is thus an important design principle for achieving higher efficiencies in those electrophosphorescent organic light-emitting diodes for which the triplet energy levels of the host and guest are similar
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
A study with 114 young adults investigated the correlations of intelligence factors and working-memory capacity with reaction time (RT) tasks. Within two sets of four-choice RT tasks, stimulus-response compatibility was varied over three levels: compatible, incompatible, and arbitrary mappings. Two satisfactory measurement models for the RTs could be established: A general factor model without constraints on the loadings and a nested model with two correlated factors, distinguishing compatible from arbitrary mappings, with constraints on the loadings. Structural models additionally including factors for working memory and intelligence showed that the nested model with correlated factors is superior in fit. Working-memory capacity and fluid intelligence were correlated strongly with the nested factor for the RT tasks with arbitrary mappings, and less with the general RT factor. The results support the hypothesis that working memory is needed to maintain arbitrary bindings between stimulus representations and response representations, and this could explain the correlation of working-memory capacity with speed in choice RT tasks
Paradigms used to study the time course of the redundant signals effect (RSE; J. O. Miller, 1986) and temporal order judgments (TOJs) share many important similarities and address related questions concerning the time course of sensory processing. The author of this article proposes and tests a new aggregate diffusion-based model to quantitatively explain both the RSE and TOJs and the relationship between them. Parametric data (13 stimulus onset asynchronies) from an experiment with pairs of visual stimuli (626-nm LEDs) confirm that, relative to central signals (3 degrees), peripheral signals (35 degrees) yield slower reaction times, more strongly modulated RSE time-course functions, and flatter TOJ psychometric functions. All of these qualitative features are well captured, even in quantitative detail, by the aggregate diffusion model.
We study thermally induced birefringence in crystalline Nd:YAG zigzag slab lasers and the associated depolarization losses. The optimum crystallographic orientation of the zigzag slab within the Nd:YAG boule and photoelastic effects in crystalline Nd:YAG slabs are briefly discussed. The depolarization is evaluated using the temperature and stress distributions, calculated using a finite element model, for realistically pumped and cooled slabs of finite dimensions. Jones matrices are then used to calculate the depolarization of the zigzag laser mode. We compare the predictions with measurements of depolarization, and suggest useful criteria for the design of the gain media for such lasers.
High cw power using an external cavity for spectral beam combining of diode laser-bar emission
(2006)
In extension to known concepts of wavelength-multiplexing diode laser arrays, a new external cavity is presented. The setup simultaneously improves the beam quality of each single emitter of a standard 25 emitter broad-area stripe laser bar and spectrally superimposes the 25 beams into one. By using this external resonator in an "off-axis" arrangement, beam qualities of M-slow(2) < 14 and M-fast(2) < 3 with optical powers in excess of 10 W in cw operation are obtained.
We analyze the notions of monotonicity and complete monotonicity for Markov Chains in continuous-time, taking values in a finite partially ordered set. Similarly to what happens in discrete-time, the two notions are not equivalent. However, we show that there are partially ordered sets for which monotonicity and complete monotonicity coincide in continuous time but not in discrete-time
Diagnosis and repair of negative polarity constructions in the light of symbolic resonance analysis
(2006)
in a post hoc analysis, we investigate differences in event-related potentials of two studies (Drenhaus et al., 2004, to appear; Saddy et al., 2004) by using the symbolic resonance analysis (Beim Graben & Kurths, 2003). The studies under discussion, examined the failure to license a negative polarity item (NPI) in German: Saddy et al. (2004a) reported an N400 component when the NPI was not accurately licensed by negation; Drenhaus et al. (2004, to appear) considered additionally the influence of constituency of the licensor in NPI constructions. A biphasic N400-P600 response was found for the two induced violations (the lack of licensor and the inaccessibility of negation in a relative clause). The symbolic resonance analysis (SRA) revealed an effect in the P600 time window for the data in Saddy et al., which was not found by using the averaging technique. The SRA of the ERPs in Drenhaus et al., showed that the P600 components are distinguishable concerning the amplitude and latency. It was smaller and earlier in the condition where the licensor is inaccessible, compared to the condition without negation in the string. Our findings suggest that the failure in licensing NPIs is not exclusively related to semantic integration costs (N400). The elicited P600 components reflect differences in syntactic processing. Our results confirm and replicate the effects of the traditional voltage average analysis and show that the SRA is a useful tool to reveal and pull apart ERP differences which are not evident using the traditional voltage average analysis.
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
New amphiphilic diblock copolymers : surfactant properties and solubilization in their micelles
(2006)
Several series of amphiphilic diblock copolymers are investigated as macrosurfactants in comparison to reference low-molar-mass and polymeric surfactants. The various copolymers share poly(butyl acrylate) as a common hydrophobic block but are distinguished by six different hydrophilic blocks (one anionic, one cationic, and four nonionic hydrophilic blocks) with various compositions. Dynamic light scattering experiments indicate the presence of micelles over the whole concentration range from 10(-4) to 10 g(.)L(-1). Accordingly, the critical micellization concentrations are very low. Still, the surface tension of aqueous solutions of block copolymers decreases slowly but continuously with increasing concentration, without exhibiting a plateau. The longer the hydrophobic block, the shorter the hydrophilic block, and the less hydrophilic the monomer of the hydrophilic block is, the lower the surface tension is. However, the effects are small, and the copolymers reduce the surface tension much less than standard low-molar-mass surfactants. Also, the copolymers foam much less and even act as anti-foaming agents in classical foaming systems composed of standard surfactants. The copolymers stabilize O/W emulsions made of methyl palmitate as equally well as standard surfactants but are less efficient for O/W emulsions made of tributyrine. However, the copolymer micelles exhibit a high solubilization power for hydrophobic dyes, probably at their core-corona interface, in dependence on the initial geometry of the micelles and the composition of the block copolymers. Whereas micelles of copolymers with strongly hydrophilic blocks are stable upon solubilization, solubilization-induced micellar growth is observed for copolymers with moderately hydrophilic blocks
Finding non-Gaussian components of high-dimensional data is an important preprocessing step for efficient information processing. This article proposes a new linear method to identify the '' non-Gaussian subspace '' within a very general semi-parametric framework. Our proposed method, called NGCA (non-Gaussian component analysis), is based on a linear operator which, to any arbitrary nonlinear (smooth) function, associates a vector belonging to the low dimensional non-Gaussian target subspace, up to an estimation error. By applying this operator to a family of different nonlinear functions, one obtains a family of different vectors lying in a vicinity of the target space. As a final step, the target space itself is estimated by applying PCA to this family of vectors. We show that this procedure is consistent in the sense that the estimaton error tends to zero at a parametric rate, uniformly over the family, Numerical examples demonstrate the usefulness of our method
In the estimate of dispersion with the help of wavelet analysis considerable emphasis has been put on the extraction of the group velocity using the modulus of the wavelet transform. In this paper we give an asymptotic expression of the full propagator in wavelet space that comprises the phase velocity as well. This operator establishes a relationship between the observed signals at two different stations during wave propagation in a dispersive and attenuating medium. Numerical and experimental examples are presented to show that the method accurately models seismic wave dispersion and attenuation
We report measurements of radial and azimuthal anisotropy in the tipper mantle beneath southern and central Finland, which we obtained by array analysis of fundamental-mode Rayleigh and Love waves. Azimuthally averaged phase velocities were analysed in the period range 15 to 190 s for Rayleigh waves and 15 to 100 s for Love waves. The azimuthal variation of the Rayleigh wave phase velocities was obtained in the period range 20 to 100s. The limited depth resolution of fundamental-mode surface waves necessitated strong damping constraints in the inversion for anisotropic parameters. We investigated the effects of non-unicity on the final model by experimenting with varying model geometries. The radial anisotropy beneath Finland can be explained by a lithosphere at least 200km thick, predominantly (> 50% by volume) composed of olivine crystals having their a-axes randomly distributed in the horizontal plane. On the contrary, the measured lithospheric azimuthal anisotropy is small. This call be reconciled with body-wave observations made in the area that indicate a complex pattern of rapidly varying anisotropy. Below 200-250km depth, that is below the petrologic lithosphere as revealed by xenolith analyses conducted in the area, the magnitude of the azimuthal anisotropy increases and would be compatible with a mantle containing 15-20% by volume of olivine crystals whose a-axes are coherently aligned in the N-NE direction. The alignment of the a-axes is off the direction of present-day absolute plate motion in either the no-net-rotation or hot-spot reference frame, currently N55-N60. We interpret this mismatch as evidence for a complex convective flow pattern of the mantle beneath the shield, which, by inference, is decoupled from the overlying lithosphere.
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
A free-ranging bushbuck (Tragelaphus scriptus) population was observed over a period of 3 years, thereby enabling a detailed description of the behavioural repertoire of this widespread but barely investigated solitary African antelope species. Agonistic and submissive behaviour patterns are described, among them several hitherto un- described behaviour patterns - such as "escorting", where territorial males guide intruders to the periphery of their territory - and "push-up position", an extreme form of submissive behaviour. Furthermore, we report on behaviour patterns of males and females during mating as well as on behaviour patterns of parents directed towards their offspring. Again, we describe a hitherto unknown behaviour: the protection of calves by adult males, which may be a socio-positive behaviour directed towards their offspring led by kin selection
What makes computer users spend their free time working with the computer? Are there different types of users and, if so, in what ways do they differ? N = 271 subjects took part in an online survey concerning the incentives for computer use in free time. Selected mailing lists were used to identify highly committed users (A4 3.9 hours of free time a day spent working with computers). The following incentive factors were found for these users: community/ affiliation; sense of competence; flexibility/utility; avoidance of boredom; rebellious tendency to illegality. Depending on their favorite use of the computer, three types of users were found: Purposeful users (58%), hackers (entering other networks without intention to cause damage) (22%), and crackers (entering other networks with intention to cause damage) (20%). There are significant differences in the incentive profiles of these types of users. Hacking and cracking, but not purposeful use, are correlated with flow experience and positive activation. These findings are not representative for all leisure time computer users. They refer to a sample of highly committed users who can be reached in special associations (e.g., relevant student networks, the Chaos Computer Club)
The crystal and molecular structures of sodium and barium complexes of dibenzo-24-crown-8 ether
(2006)
The sodium and barium isothiocyanate complexes of 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydrodibenzo[b,n]- 1,4,7,10,13,16,19,22-octaoxacyclotetracosin (dibenzo-24-crown-8 ether = DB24C8) were synthesized and analyzed by X-ray diffraction. The sodium complex, [Na(DB24C8)(NCS)(H2O)] 1, crystallizes in the orthorhombic space group Fdd2 with 16 molecules in the unit cell. The coordination number of Na is 6 and the central ion is located in a distorted octahedric environment. Only four of the crown ether oxygen atoms are involved. The coordination polyhedron is completed by the isothiocanate anion and by a water molecule, which is stabilized by hydrogen bonds. The barium complex, [Ba(DB24C8)(NCS)(2)] 2, crystallizes in the trigonale space group P3(1)21 with 3 molecules in the unit cell. Crystallographic C-2 symmetry is observed for the complex. The coordination number of Ba is 10. Barium is coordinated with the eight oxygen atoms of the macrocyclic ligand and with two isothiocyanate anions. The absolute structure was estimated using the FLACK parameter
In the humid tropics, continuing high deforestation rates are seen alongside an increasing expansion of secondary forests. In order to understand and model the consequences of these dynamic land-use changes for regional water cycles, the response of soil hydraulic properties to forest disturbance and recovery has to be quantified.At a site in the Brazilian Amazonia, we annually monitored soil infiltrability and saturated hydraulic conductivity (K-s) at 12.5, 20 cm, and 50 cm soil depth after manual forest conversion to pasture (year zero to four after pasture establishment), and during secondary succession after pasture abandonment (year zero to seven after pasture abandonment). We evaluated the hydrological consequences of the detected changes by comparing the soil hydraulic properties with site-specific rainfall intensities and hydrometric observations. Within one year after grazing started, infiltrability and K-s at 12.5 and 20 cm depth decreased by up to one order of magnitude to levels which are typical for 20-year-old pasture. In the three subsequent monitoring years, infiltrability and K-s remained stable. Land use did not impact on subsoil permeability. Whereas infiltrability values are large enough to allow all rainwater to infiltrate even after the conversion, the sudden decline of near-surface K-s is of hydrological relevance as perched water tables and overland flow occur more often on pastures than in forests at our study site. After pasture abandonment and during secondary succession, seven years of recovery did not suffice to significantly increase infiltrability and K-s at 12.5 depth although a slight recovery is obvious. At 20 cm soil depth, we detected a positive linear increase within the seven-year time frame but annual means did not differ significantly. Although more than a doubling of infiltrability and K-s is still required to achieve pre-disturbance levels, which will presumably take more than a decade, the observed slight increases of K-s might already decrease the probability of perched water table generation and overland flow development well before complete recovery.
Penicillin amidase from Alacaligenes faecalis is an attractive biocatalyst for hydrolysis of penicillin G for production of 6-aminopenicillanic acid, which is used in the synthesis of semi-synthetic beta-lactam antibiotics. Recently a mutant of this enzyme with extended C-terminus of the A-chain comprising parts of the connecting linker peptide was constructed. Its turnover number for the hydrolysis of penicillin G was 140 s(-1), about twice of the value for the wild-type enzyme (80 s(-1)). At the same time the specificity constant was improved about three-fold. The wild- type and the mutant enzymes showed similar pH stability suggesting that the linker peptide fragment covalently attached to the A-chain does not alter the electrostatic interactions in the protein core. Although the global stability of A. faecalis wild-type enzyme and the T206GS213G variant does not differ, the presence of the linker fragment stabilizes the domains interface, as evidenced by the monophasic transition of the mutant enzyme from folded to unfolded state during urea-induced denaturation. The high stability and activity of the mutant enzyme provides a rationale to use it as a biocatalyst in the industrial processes, where the enzyme must be more robust to fluctuations in the operational conditions.
We present a detailed, realistic analysis of the implementation of a proposal for a quantum phase gate based on atomic vibrational states, specializing it to neutral rubidium atoms on atom chips. We show how to create a double-well potential with static currents on the atom chips, using for all relevant parameters values that are achieved with present technology. The potential barrier between the two wells can be modified by varying the currents in order to realize a quantum phase gate for qubit states encoded in the atomic external degree of freedom. The gate performance is analyzed through numerical simulations; the operation time is similar to 10 ms with a performance fidelity above 99.9%. For storage of the state between the operations the qubit state can be transferred efficiently via Raman transitions to two hyperfine states, where its decoherence is strongly inhibited. In addition we discuss the limits imposed by the proximity of the surface to the gate fidelity.
The acinar salivary glands of cockroaches receive a dual innervation from the subesophageal ganglion and the stomatogastric nervous system. Acinar cells are surrounded by a plexus of dopaminergic and serotonergic varicose fibers. In addition, seroton-ergic terminals lie deep in the extracellulor spaces between acinar cells. Excitation-secretion coupling in cockroach salivary glands is stimulated by both dopamine and serotonin. These monoamines cause increases in the intracellular concentrations of cAMP and Ca2+. Stimulation of the glands by serotonin results in the production of a protein-rich saliva, whereas stimulation by dopamine results in saliva that is protein-free. Thus, two elementary secretary processes, namely electrolyte/water secretion and protein secretion, are triggered by different aminergic transmitters. Because of its simplicity and experimental accessibility, cockroach salivary glands have been used extensively as a model system to study the cellular actions of biogenic amines and to examine the pharmacological properties of biogenic amine receptors. In this review, we summarize current knowledge concerning the aminergic control of cockroach salivary glands and discuss our efforts to characterize Periplaneta biogenic amine receptors molecularly
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.
In this Letter, we show that coherence and phase synchronization analysis are sensitive but not specific in detecting the correct class of underlying dynamics. We propose procedures to increase specificity and demonstrate the power of the approach by application to paradigmatic dynamic model systems. (c) 2006 Elsevier B.V. All rights reserved
A new synthetic approach to 2,3-dihydro-4H-1,3-thiazine derivatives based upon reductive rearrangement of 1,2- dithiole-3-ylidene thiones has been developed. In turn, the 1,2-dithiole derivatives were prepared by an efficient ring- opening-closing process of 2-alkylidene-4-oxothiazolidines, induced in the presence of Lawesson's reagent by intramolecular non-bonded 1,5-type S...O interactions in the 4-oxothiazolidine precursors.
Major earthquakes ( M > 8) have repeatedly ruptured the Nazca-South America plate interface of south-central Chile involving meter scale land-level changes. Earthquake recurrence intervals, however, extending beyond limited historical records are virtually unknown, but would provide crucial data on the tectonic behavior of forearcs. We analyzed the spatiotemporal pattern of Holocene earthquakes on Santa Maria Island (SMI; 37 degrees S), located 20 km off the Chilean coast and approximately 70 km east of the trench. SMI hosts a minimum of 21 uplifted beach berms, of which a subset were dated to calculate a mean uplift rate of 2.3 +/- 0.2 m/ky and a tilting rate of 0.022 +/- 0.002 degrees/ky. The inferred recurrence interval of strandline-forming earthquakes is similar to 180 years. Combining coseismic uplift and aseismic subsidence during an earthquake cycle, the net gain in strandline elevation in this environment is similar to 0.4 m per event
We report here for the first time on surface immobilization of hollow faceted polyhedrons formed from catanionic surfactant mixtures. We find that electrostatic interaction with the substrate dominates their adhesion behavior. Using polyelectrolyte coated surfaces with tailored charge densities, polyhedrons can thus be immobilized without complete spreading, which allows for further study of their mechanical properties using AFM force measurements. The elastic response of individual polyhedrons can be locally resolved, showing pronounced differences in stiffness between faces and vertexes of the structure, which makes these systems interesting as models for structurally similar colloidal scale objects such as viruses, where such effects are predicted but cannot be directly observed due to the smaller dimensions. Elastic constants of the wall material are estimated using shell and plate deformation models and are found to be a factor of 5 larger than those for neutral lipidic bilayers in the gel state. We discuss the molecular origins of this high stiffness
An amperometric biosensor for the determination of glycated hemoglobin in human whole blood is proposed. The principle is based on the electrochemical measurement of ferroceneboronic acid (FcBA) that has been specifically bound to the glycated N-terminus. Hemoglobin is immobilized on a zirconium dioxide nanoparticle modified pyrolytic graphite electrode (PGE) in the presence of didodecyldimethylammonium bromide (DDAB). The incubation of this sensor in FcBA solution leads to the formation of an FcBA-modified surface due to the affinity interaction between boronate and the glycated sites of the hemoglobin. The binding of FcBA results in well-defined redox peaks with an E-0' of 0.299 V versus Ag/AgCl (1 M KCl). The square wave voltammetric response of the bound FcBA reflects the amount of glycated hemoglobin at the surface. This signal increases linearily with the degree of glycated hemoglobin from 6.8 to 14.0% of total immobilized hemoglobin. The scheme was applied to the determination of the fraction of glycated hemoglobin in whole blood samples.
Non-stationarities are ubiquitous in EEG signals. They are especially apparent in the use of EEG-based brain- computer interfaces (BCIs): (a) in the differences between the initial calibration measurement and the online operation of a BCI, or (b) caused by changes in the subject's brain processes during an experiment (e.g. due to fatigue, change of task involvement, etc). In this paper, we quantify for the first time such systematic evidence of statistical differences in data recorded during offline and online sessions. Furthermore, we propose novel techniques of investigating and visualizing data distributions, which are particularly useful for the analysis of (non-) stationarities. Our study shows that the brain signals used for control can change substantially from the offline calibration sessions to online control, and also within a single session. In addition to this general characterization of the signals, we propose several adaptive classification schemes and study their performance on data recorded during online experiments. An encouraging result of our study is that surprisingly simple adaptive methods in combination with an offline feature selection scheme can significantly increase BCI performance
The iron-containing ionic liquid (IL) 1-butyl-3-methylimidazolium tetrachloroferrate(III) [Bmim][FeCl4] has been used as a building block in the synthesis of transparent, ion-conducting, and paramagnetic ionogels. UV/Vis spectroscopy shows that the coordination around the Fe(III) ion does slightly change upon incorporation of the IL into PMMA. The thermal stability of the PMMA increases significantly with IL incorporation. In particular, the onset weight loss observed at ca. 265 degrees C for pure PMMA is completely suppressed. The ionic conductivity shows a strong temperature dependence and increases with increasing IL weight fractions. The magnetic properties are similar to those reported for the pure IL and are not affected by the incorporation into the PMMA matrix. The resulting ionogel is thus an interesting prototype for soft, flexible, and transparent materials combining the mechanical properties of the matrix with the functionality of the metal-containing IL, such as magnetism.
In this work, ion mobility (IM) spectra of more than 50 aromatic compounds were recorded with a laser-based IM spectrometer at atmospheric pressure. IM spectra of PAH in the laser desorption experiment show a high complexity resulting from the occurrence of monomeric, dimeric, and oligomeric cluster ions. The mobilities of all compounds were determined in helium as drift gas. This allows the calculation of the diffusion cross sections (Omega(calc)) on the basis of the exact hard sphere scattering model and their comparison with the experimentally determined diffusion cross sections (Omega(exp)). Extended Omega(exp)/Omega(calc) and Omega(exp/)mass correlations were performed in order to gain insight into conformational properties of cationic alkyl benzenes and internal rotation of phenyl rings in aromatic ions. This is demonstrated with some examples, such as the evaluation of the dihedral angle of the ions of 9,10- diphenylanthracene, o- and m-terphenyl, and 1,2,3- and 1,3,5-triphenylbenzene. Furthermore, sandwich and T-structures of dimeric PAH cations are discussed. The analysis was extended to oligomeric ions with up to nine monomer units. Experimental evidence is presented suggesting the formation of pi-stacks with a transition toward modified pi-stacks with increasing cluster size. The distance between monomeric units in dimeric and oligomeric ions was obtained
Predictive habitat models are an important tool for ecological research and conservation. A major cause of unreliable models is excessive model complexity, and regularization methods aim to improve the predictive performance by adequately constraining model complexity. We compare three regularization methods for logistic regression: variable selection, lasso, and ridge. They differ in the way model complexity is measured: variable selection uses the number of estimated parameters, the lasso uses the sum of the absolute values of the parameter estimates, and the ridge uses the sum of the squared values of the parameter estimates. We performed a simulation study with environmental data of a real landscape and artificial species occupancy data. We investigated the effect of three factors on relative model performance: (1) the number of parameters (16, 10, 6, 2) in the 'true' model that determined the distribution of the artificial species, (2) the prevalence, i.e. the proportion of sites occupied by the species, and (3) the sample size (measured in events per variable, EPV). Regularization improved model discrimination and calibration. However, no regularization method performed best under all circumstances: the ridge generally performed best in the 16-parameter scenario. The lasso generally performed best in the 10-parameter scenario. Variable selection with AIC was best at large sample sizes (EPV >= 10) when less than half of the variables influenced the species distribution. However, at low sample sizes (EPV < 10), ridge and lasso always performed best, regardless of the parameter scenario or prevalence. Overall, calibration was best in ridge models. Other methods showed overconfidence, particularly at low sample sizes. The percentage of correctly identified models was low for both lasso and variable selection. Variable selection should be used with caution. Although it can produce the best performing models under certain conditions, these situations are difficult to infer from the data. Ridge and lasso are risk-averse model strategies that can be expected to perform well under a wide range of underlying species-habitat relationships, particularly at small sample sizes.
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
An effective dynamical description of a general class of stochastic phase oscillators is presented. For this, the effective phase velocity is defined either by the stochastic phase oscillators invariant probability density or its first passage times. Using the first approach the effective phase exhibits the correct frequency and invariant distribution density, whereas the second approach models the proper phase resetting curve. The discrepancy of the effective models is most pronounced for noise-induced oscillations and is related to non-monotonicity of the stochastic phase variable due to fluctuations.
In this paper, a measuring technique is presented for the detection of radial oscillations of tube walls excited by changes in internal air pressure. On organ pipes, the oscillations were investigated by means of piezoelectric polymer films slightly tensioned around the pipe bodies. Employing sensors with patterned electrodes, the well-known elliptical oscillation of the cross section as well as an additional monopole breathing of the organ-pipe body were detected. For the monopole breathing, a close relationship between the pressure distribution of the air-column resonances inside the pipe and the circumference variations along the pipe was observed
Human comment is studied using data from 'tianya' which is one of the most popular on-line social systems in China. We found that the time interval between two consecutive comments on the same topic, called inter-event time, follows a power-law distribution. This result shows that there is no characteristic decay time on a topic. It allows for very long periods without comments that separate bursts of intensive comments. Furthermore, the frequency of a different ID commenting on a topic also follows a power-law distribution. It indicates that there are some "hubs" in the topic who lead the direction of the public opinion. Based on the personal comments habit, a model is introduced to explain these phenomena. The numerical simulations of the model fit well with the empirical results. Our findings are helpful for discovering regular patterns of human behavior in on-line society and the evolution of the public opinion on the virtual as well as real society.
Even during visual fixation of a stationary target, our eyes perform rather erratic miniature movements, which represent a random walk. These "fixational" eye movements counteract perceptual fading, a consequence of fast adaptation of the retinal receptor systems to constant input. The most important contribution to fixational eye movements is produced by microsaccades; however, a specific function of microsaccades only recently has been found. Here we show that the occurrence of microsaccades is correlated with low retinal image slip approximate to 200 ms before microsaccade onset. This result suggests that microsaccades are triggered dynamically, in contrast to the current view that microsaccades are randomly distributed in time characterized by their rate-of-occurrence of 1 to 2 per second. As a result of the dynamic triggering mechanism, individual microsaccade rate can be predicted by the fractal dimension of trajectories. Finally, we propose a minimal computational model for the dynamic triggering of microsaccades
The coherence length of the thermal electromagnetic field near a planar surface has a minimum value related to the nonlocal dielectric response of the material. We perform two model calculations of the electric energy density and the field's degree of spatial coherence. Above a polar crystal, the lattice constant gives the minimum coherence length. It also gives the upper limit to the near field energy density, cutting off its 1/z(3) divergence. Near an electron plasma described by the semiclassical Lindhard dielectric function, the corresponding length scale is fixed by plasma screening to the Thomas-Fermi length. The electron mean free path, however, sets a larger scale where significant deviations from the local description are visible
We develop an effective description of noise-induced oscillations based on deterministic phase dynamics. The phase equation is constructed to exhibit correct frequency and distribution density of noise-induced oscillations. In the simplest one-dimensional case the effective phase equation is obtained analytically, whereas for more complex situations a simple method of data processing is suggested. As an application an effective coupling function is constructed that quantitatively describes periodically forced noise-induced oscillations.
The article departs from the discussion of the Sources of the scholar interest in civil societv and proceeds to the functional expectations about it. It claims that the concept of civil society, as it is frequently used in scientific and political debates, has specific cultural roots, which makcs a trans-cultural analysis difficult or perhaps even impossible. Furthermore, the article addresses three conceptual problems of civil society, namely the issue of what constitutes civil society, its autonomy and impact as well as the challenge of civil society to the state. The central argument of the article is that in order to examine the impact of civil society on governance and democracy, it is recommendable to include three levels of analysis, namely the structure and functions of civil society (including also the possibly negative impact of civil society), the type of state co-existing with civil society as well as the character of the relationship between state and civil society
Three ODP sites located on the Marion Plateau, Northeast Australian margin, were investigated for clay mineral and bulk mineralogy changes through the early to middle Miocene. Kaolinite to smectite (K/S) ratios, as well as mass accumulation rates of clays, point to a marked decrease in accumulation of smectite associated with an increase in accumulation of kaolinite starting at similar to 15.6 Ma, followed by a, second increase in accumulation of kaolinite at similar to 13.2 Ma. Both of these increases are correlative to an increase in the calcite to detritus ratio. Comparison of our record with published precipitation proxies from continental Queensland indicates that increases in kaolinite did not correspond to more intense tropical-humid conditions, but instead to periods of greater aridity. Three mechanisms are explored to explain the temporal trends in clad, on the Marion Plateau: sea-level changes, changes in oceanic currents, and denudation of the Australian continent followed by reworking and eolian transport of clays. Though low mass accumulation rates of kaolinite are compatible with a possible contribution of eolian material after 14 Ma, when Australia became more arid, the lateral distribution of kaolinite along slope indicates mainly fluvial input for all clays and thus rules out this mechanism as well as oceanic current transport as the main controls behind clay accumulation on the plateau. We propose a model explaining the good correlation between long-term sea-level fall, decrease in smectite accumulation, increase in kaolinite accumulation and increase in carbonate input to the distal slope locations. We hypothesize that during low sea level and thus periods of drier continental climate in Queensland, early Miocene kaolinite-rich lacustrine deposits were being reworked, and that the progradation of the heterozoan carbonate platforms towards the basin center favored input of carbonate to the distal slope sites. The major find of our study is that increase kaolinite fluxes on the Queensland margin during the early and middle Miocene did not reflect the establishment of a tropical climate, and this stresses that care must be taken when reconstructing Australian climate based on deep-sea clay records alone.
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
Quenching of the triplet state of tryptophan by cysteine has provided a new tool for measuring the rate of forming a specific intramolecular contact in disordered polypeptides. Here, we use this technique to investigate contact formation in the denatured state of CspTm, a small cold-shock protein from Thermotoga maritima, engineered to contain a single tryptophan residue (W29) and a single cysteine residue at the C terminus (C67). At all concentrations of denaturant, the decay rate of the W29 triplet of the unfolded protein is more than tenfold faster than the rate observed for the native protein (not, vert, similar104 s;1). Experiments on the unfolded protein without the added C- terminal cysteine residue show that this faster rate results entirely from contact quenching by C67. The quenching rate in the unfolded state by C67 increases at concentrations of denaturant that favor folding, indicating a compaction of the unfolded protein as observed previously in single-molecule Foerster resonance energy transfer (FRET) experiments.
We report measurements on the synchronization properties of organ pipes. First, we investigate influence of an external acoustical signal from a loudspeaker on the sound of an organ pipe. Second, the mutual influence of two pipes with different pitch is analyzed. In analogy to the externally driven, or mutually coupled self-sustained oscillators, one observes a frequency locking, which can be explained by synchronization theory. Further, we measure the dependence of the frequency of the signals emitted by two mutually detuned pipes with varying distance between the pipes. The spectrum shows a broad '' hump '' structure, not found for coupled oscillators. This indicates a complex coupling of the two organ pipes leading to nonlinear beat phenomena.
A methodology is presented to assess the impact of reservoir silting oil water availability for semiarid environments, applied to seven representative watersheds in the state of Ceara, Brazil. Water yield is computed using stochastic modelling for several reliability levels and water yield reduction is quantified for the focus areas. The yield-volume elasticity concept, which indicates the relative yield reduction in terms of relative storage capacity of the reservoirs, is presented and applied. Results chow that storage capacity was reduced by 0.2% year(-1) due to silting, that the risk of water shortage almost doubled in less than 50 years for the most critical reservoir, and that reduction of storage capacity had three times more impact oil yield reduction than the increase in evaporation. Average 90% reliable yield-volume elasticity was 0.8, which means that the global water yield (Q(90)) in Ceara is expected to diminish yearly by 388 L s(-1) due to reservoir silting
Employing the chemically passive carbon reconstruction W(110)/C-R(15x3) as substrate for deposition of C-60 molecules, we have discovered by scanning tunneling microscopy two-dimensional self-assembly of fullerenes into uniform molecular nanoclusters with "magic" numbers. Our photoemission measurements determine van der Waals forces as the dominating interaction in this self-organizing two-dimensional molecular gas. Based on this, a theoretical determination of the cluster structures in the framework of the Girifalco model gives perfect agreement with the experiment