TY - JOUR A1 - Burchert, Frank A1 - Hanne, Sandra A1 - Vasishth, Shravan T1 - Sentence comprehension disorders in aphasia the concept of chance performance revisited JF - Aphasiology : an international, interdisciplinary journal N2 - Background: In behavioural tests of sentence comprehension in aphasia, correct and incorrect responses are often randomly distributed. Such a pattern of chance performance is a typical trait of Broca's aphasia, but can be found in other aphasic syndromes as well. Many researchers have argued that chance behaviour is the result of a guessing strategy, which is adopted in the face of a syntactic breakdown in sentence processing. Aims: Capitalising on new evidence from recent studies investigating online sentence comprehension in aphasia using the visual world paradigm, the aim of this paper is to review the concept of chance performance as a reflection of a syntactic impairment in sentence processing and to re-examine the conventional interpretation of chance performance as a guessing behaviour. Main Contribution: Based on a review of recent evidence from visual world paradigm studies, we argue that the assumption of chance performance equalling guessing is not necessarily compatible with actual real-time parsing procedures in people with aphasia. We propose a reinterpretation of the concept of chance performance by assuming that there are two distinct processing mechanisms underlying sentence comprehension in aphasia. Correct responses are always the result of normal-like parsing mechanisms, even in those cases where the overall performance pattern is at chance. Incorrect responses, on the other hand, are the result of intermittent deficiencies of the parser. Hence the random guessing behaviour that persons with aphasia often display does not necessarily reflect a syntactic breakdown in sentence comprehension and a random selection between alternatives. Instead it should be regarded as a result of temporal deficient parsing procedures in otherwise normal-like comprehension routines. Conclusion: Our conclusion is that the consideration of behavioural offline data alone may not be sufficient to interpret a performance in language tests and subsequently draw theoretical conclusions about language impairments. Rather it is important to call on additional data from online studies that look at language processing in real time in order to gain a comprehensive picture about syntactic comprehension abilities of people with aphasia and possible underlying deficits. KW - Sentence comprehension in aphasia KW - Chance performance KW - Visual world paradigm KW - Eye tracking KW - Online sentence processing Y1 - 2013 U6 - https://doi.org/10.1080/02687038.2012.730603 SN - 0268-7038 VL - 27 IS - 1 SP - 112 EP - 125 PB - Wiley CY - Hove ER - TY - JOUR A1 - Mühlbauer, Thomas A1 - Besemer, Carmen A1 - Wehrle, Anja A1 - Gollhofer, Albert A1 - Granacher, Urs T1 - Relationship between strength; balance and mobility in children aged 7-10 years JF - Gait & posture N2 - The purpose of this study was to investigate the association between variables of lower extremity muscle strength, balance, and mobility assessed under various task conditions. Twenty-one healthy children (mean age: 9 +/- 1 years) were tested for their isometric and dynamic strength as well as for their steady-state, proactive, and reactive balance and mobility. Balance and mobility tests were conducted under single and dual task conditions. Significant positive correlations were detected between measures of isometric and dynamic leg muscle strength. Hardly any significant associations were observed between variables of strength and balance/mobility and between measures of steady-state, proactive, and reactive balance. Additionally, no significant correlations were detected between balance/mobility tests performed under single and dual task conditions. The predominately non-significant correlations between different balance components and mobility imply that balance and mobility performance is task specific. Further, strength and balance/mobility as well as balance under single and dual task conditions seem to be independent of each other and may have to be tested and trained complementarily. KW - Steady-state balance KW - Proactive/reactive balance KW - Maximal isometric force KW - Jumping height KW - Single/dual tasking KW - Cognitive/motor interference Y1 - 2013 U6 - https://doi.org/10.1016/j.gaitpost.2012.06.022 SN - 0966-6362 VL - 37 IS - 1 SP - 108 EP - 112 PB - Elsevier CY - Clare ER - TY - JOUR A1 - Wissel, Jörg A1 - Manack, Aubrey A1 - Brainin, Michael T1 - Toward an epidemiology of poststroke spasticity JF - Neurology : official journal of the American Academy of Neurology N2 - Poststroke spasticity (PSS)-related disability is emerging as a significant health issue for stroke survivors. There is a need for predictors and early identification of PSS in order to minimize complications and maladaptation from spasticity. Reviewing the literature on stroke and upper motor neuron syndrome, spasticity, contracture, and increased muscle tone measured with the Modified Ashworth Scale and the Tone Assessment Scale provided data on the dynamic time course of PSS. Prevalence estimates of PSS were highly variable, ranging from 4% to 42.6%, with the prevalence of disabling spasticity ranging from 2% to 13%. Data on phases of the PSS continuum revealed evidence of PSS in 4% to 27% of those in the early time course (1-4 weeks poststroke), 19% to 26.7% of those in the postacute phase (1-3 months poststroke), and 17% to 42.6% of those in the chronic phase (>3 months poststroke). Data also identified key risk factors associated with the development of spasticity, including lower Barthel Index scores, severe degree of paresis, stroke-related pain, and sensory deficits. Although such indices could be regarded as predictors of PSS and thus enable early identification and treatment, the different measures of PSS used in those studies limit the strength of the findings. To optimize evaluation in the different phases of care, the best possible assessment of PSS would make use of a combination of indicators for clinical impairment, motor performance, activity level, quality of life, and patient-reported outcome measures. Applying these recommended measures, as well as increasing our knowledge of the physiologic predictors of PSS, will enable us to perform clinical and epidemiologic studies that will facilitate identification and early, multimodal treatment. Y1 - 2013 SN - 0028-3878 VL - 80 IS - 1 SP - S13 EP - S19 PB - Lippincott Williams & Wilkins CY - Philadelphia ER - TY - JOUR A1 - Richter, Michael A1 - van Hout, Roeland T1 - Interpreting resultative sentences in German BT - stages in L1 acquisition JF - Linguistics : an interdisciplinary journal of the language sciences N2 - This article presents the results of a study on the interpretation and acceptance of adjectival resultatives of German children between 6 and 9 years of age and adults. These results brought to light significant differences, due to age, in the interpretation and acceptance of these resultatives, that is to say, sentences with an adjective in the final position. The youngest participants were prone to accept ungrammatical sentences by assigning a resultative meaning. The ungrammaticality of the sentences in question was not due to semantic inconsistencies but to violations of the selectional properties of verbs, as for instance in *die Kinder erschrecken die Katze angstlich 'the children frighten the cat scared'. In contrast, the adults rejected or amended those sentences. The conclusion is (a) that the children seemed to rely on the sentence structure as a primary cue to compute the meaning of an utterance and (b) that, in contrast with adults, the youngest children in particular had not yet learned the relevant semantic properties of verbs that determine the selectional restrictions and thus the syntactic options of verbs. This means that differences in interpretation and acceptance of sentences are due to differences in knowledge of semantic verb properties between adults and children. The relevant semantic knowledge increases in gradual stages during language acquisition. KW - first language acquisition KW - frame compliance KW - grammatical judgments KW - verb classes KW - resultative sentences Y1 - 2013 U6 - https://doi.org/10.1515/ling-2013-0004 SN - 0024-3949 VL - 51 IS - 1 SP - 117 EP - 144 PB - De Gruyter Mouton CY - Berlin ER - TY - JOUR A1 - Kranich, Svenja T1 - Functional layering and the English progressive JF - Linguistics : an interdisciplinary journal of the language sciences N2 - In this article, it will be argued that the concept of functional layering - an extension of Hopper's (1991) concept of layering - can be fruitfully applied to understand the mechanisms behind the sometimes large and messy looking synchronic picture of diverse meanings which one and the same construction can fulfill at a particular point in time. The concept will be used to account for the meaning spectrum of the present-day English progressive, which, it will be argued, no monosemic approach to date can account for. Taking a look at the diachrony of the construction will help to reveal that the various "exceptions" found in the use of the progressive can be understood as reflections of different stages in its development. Older, less grammaticalized or less well-defined usage patterns thus often survive in certain restricted niches next to the newer, more grammaticalized or more clear-cut functions, representing different diachronic layers. In addition to this diachronic motivation for synchronic meaning variety, the article will also address the crucial question of how a present-day hearer of a progressive form is able to decode the specific meaning intended by the speaker based on contextual clues. The article ends with some suggestions for further applications of the concept of functional layering. KW - grammaticalization KW - subjectification KW - semantic change KW - the English progressive construction KW - polysemy Y1 - 2013 U6 - https://doi.org/10.1515/ling-2013-0001 SN - 0024-3949 VL - 51 IS - 1 SP - 1 EP - 32 PB - De Gruyter Mouton CY - Berlin ER - TY - JOUR A1 - Hammer, Conny A1 - Ohrnberger, Matthias A1 - Faeh, Donat T1 - Classifying seismic waveforms from scratch: a case study in the alpine environment JF - Geophysical journal international N2 - Nowadays, an increasing amount of seismic data is collected by daily observatory routines. The basic step for successfully analyzing those data is the correct detection of various event types. However, the visually scanning process is a time-consuming task. Applying standard techniques for detection like the STA/LTAtrigger still requires the manual control for classification. Here, we present a useful alternative. The incoming data stream is scanned automatically for events of interest. A stochastic classifier, called hidden Markov model, is learned for each class of interest enabling the recognition of highly variable waveforms. In contrast to other automatic techniques as neural networks or support vector machines the algorithm allows to start the classification from scratch as soon as interesting events are identified. Neither the tedious process of collecting training samples nor a time-consuming configuration of the classifier is required. An approach originally introduced for the volcanic task force action allows to learn classifier properties from a single waveform example and some hours of background recording. Besides a reduction of required workload this also enables to detect very rare events. Especially the latter feature provides a milestone point for the use of seismic devices in alpine warning systems. Furthermore, the system offers the opportunity to flag new signal classes that have not been defined before. We demonstrate the application of the classification system using a data set from the Swiss Seismological Survey achieving very high recognition rates. In detail we document all refinements of the classifier providing a step-by-step guide for the fast set up of a well-working classification system. KW - Time series analysis KW - Neural networks, fuzzy logic KW - Seismic monitoring and test-ban treaty verification KW - Early warning KW - Probability distributions Y1 - 2013 U6 - https://doi.org/10.1093/gji/ggs036 SN - 0956-540X SN - 1365-246X VL - 192 IS - 1 SP - 425 EP - 439 PB - Oxford Univ. Press CY - Oxford ER - TY - JOUR A1 - Hobiger, M. A1 - Cornou, C. A1 - Wathelet, M. A1 - Di Giulio, G. A1 - Knapmeyer-Endrun, B. A1 - Renalier, F. A1 - Bard, Pierre-Yves A1 - Savvaidis, Alexandros A1 - Hailemikael, S. A1 - Le Bihan, N. A1 - Ohrnberger, Matthias A1 - Theodoulidis, N. T1 - Ground structure imaging by inversions of Rayleigh wave ellipticity sensitivity analysis and application to European strong-motion sites JF - Geophysical journal international N2 - The knowledge of the local soil structure is important for the assessment of seismic hazards. A widespread, but time-consuming technique to retrieve the parameters of the local underground is the drilling of boreholes. Another way to obtain the shear wave velocity profile at a given location is the inversion of surface wave dispersion curves. To ensure a good resolution for both superficial and deeper layers, the used dispersion curves need to cover a wide frequency range. This wide frequency range can be obtained using several arrays of seismic sensors or a single array comprising a large number of sensors. Consequently, these measurements are time-consuming. A simpler alternative is provided by the use of the ellipticity of Rayleigh waves. The frequency dependence of the ellipticity is tightly linked to the shear wave velocity profile. Furthermore, it can be measured using a single seismic sensor. As soil structures obtained by scaling of a given model exhibit the same ellipticity curve, any inversion of the ellipticity curve alone will be ambiguous. Therefore, additional measurements which fix the absolute value of the shear wave velocity profile at some points have to be included in the inversion process. Small-scale spatial autocorrelation measurements or MASW measurements can provide the needed data. Using a theoretical soil structure, we show which parts of the ellipticity curve have to be included in the inversion process to get a reliable result and which parts can be omitted. Furthermore, the use of autocorrelation or high-frequency dispersion curves will be highlighted. The resulting guidelines for inversions including ellipticity data are then applied to real data measurements collected at 14 different sites during the European NERIES project. It is found that the results are in good agreement with dispersion curve measurements. Furthermore, the method can help in identifying the mode of Rayleigh waves in dispersion curve measurements. KW - Inverse theory KW - Surface waves and free oscillations KW - Site effects KW - Computational seismology KW - Wave propagation Y1 - 2013 U6 - https://doi.org/10.1093/gji/ggs005 SN - 0956-540X VL - 192 IS - 1 SP - 207 EP - 229 PB - Oxford Univ. Press CY - Oxford ER - TY - JOUR A1 - Sachse, Rita A1 - Wüstenhagen, Doreen Anja A1 - Samalikova, Maria A1 - Gerrits, Michael A1 - Bier, Frank Fabian A1 - Kubick, Stefan T1 - Synthesis of membrane proteins in eukaryotic cell-free systems JF - Engineering in life sciences : Industry, Environment, Plant, Food N2 - Cell-free protein synthesis (CFPS) is a valuable method for the fast expression of difficult-to-express proteins as well as posttranslationally modified proteins. Since cell-free systems circumvent possible cytotoxic effects caused by protein overexpression in living cells, they significantly enlarge the scale and variety of proteins that can be characterized. We demonstrate the high potential of eukaryotic CFPS to express various types of membrane proteins covering a broad range of structurally and functionally diverse proteins. Our eukaryotic cell-free translation systems are capable to provide high molecular weight membrane proteins, fluorescent-labeled membrane proteins, as well as posttranslationally modified proteins for further downstream analysis. KW - Cell-free protein expression KW - In vitro protein synthesis KW - Labeled membrane proteins KW - Synthetic glycoprotein Y1 - 2013 U6 - https://doi.org/10.1002/elsc.201100235 SN - 1618-0240 VL - 13 IS - 1 SP - 39 EP - 48 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Häring, Tim A1 - Reger, Birgit A1 - Ewald, Jörg A1 - Hothorn, Torsten A1 - Schröder-Esselbach, Boris T1 - Predicting Ellenberg's soil moisture indicator value in the Bavarian Alps using additive georegression JF - Applied vegetation science : official organ of the International Association for Vegetation Science N2 - Questions Can forest site characteristics be used to predict Ellenberg indicator values for soil moisture? Which is the best averaged mean value for modelling? Does the distribution of soil moisture depend on spatial information? Location Bavarian Alps, Germany. Methods We used topographic, climatic and edaphic variables to model the mean soil moisture value as found on 1505 forest plots from the database WINALPecobase. All predictor variables were taken from area-wide geodata layers so that the model can be applied to some 250 000 ha of forest in the target region. We adopted methods developed in species distribution modelling to regionalize Ellenberg indicator values. Therefore, we use the additive georegression framework for spatial prediction of Ellenberg values with the R-library mboost, which is a feasible way to consider environmental effects, spatial autocorrelation, predictor interactions and non-stationarity simultaneously in our data. The framework is much more flexible than established statistical and machine-learning models in species distribution modelling. We estimated five different mboost models reflecting different model structures on 50 bootstrap samples in each case. Results Median R2 values calculated on independent test samples ranged from 0.28 to 0.45. Our results show a significant influence of interactions and non-stationarity in addition to environmental covariates. Unweighted mean indicator values can be modelled better than abundance-weighted values, and the consideration of bryophytes did not improve model performance. Partial response curves indicate meaningful dependencies between moisture indicator values and environmental covariates. However, mean indicator values <4.5 and >6.0 could not be modelled correctly, since they were poorly represented in our calibration sample. The final map represents high-resolution information of site hydrological conditions. Conclusions Indicator values offer an effect-oriented alternative to physically-based hydrological models to predict water-related site conditions, even at landscape scale. The presented approach is applicable to all kinds of Ellenberg indicator values. Therefore, it is a significant step towards a new generation of models of forest site types and potential natural vegetation. KW - Boosting KW - Mboost KW - Non-stationarity KW - Predictive vegetation mapping KW - Site ecology KW - Species distribution modelling Y1 - 2013 U6 - https://doi.org/10.1111/j.1654-109X.2012.01210.x SN - 1402-2001 VL - 16 IS - 1 SP - 110 EP - 121 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Wessig, Pablo A1 - Matthes, Annika T1 - Photochemical synthesis and properties of 1,6- and 1,8-Naphthalenophanes JF - Molecules N2 - Various 1,6- and 1,8-naphthalenophanes were synthesized by using the Photo-Dehydro-Diels-Alder (PDDA) reaction of bis-ynones. These compounds are easily accessible from omega-(3-iodophenyl)carboxylic acids in three steps. The obtained naphthalenophanes are axially chiral and the activation barrier for the atropisomerization could be determined in some cases by means of dynamic NMR (DNMR) and/or dynamic HPLC (DHPLC) experiments. KW - photo-dehydro-Diels-Alder reaction KW - naphthalenophanes KW - atropisomerism KW - dynamic NMR KW - dynamic HPLC Y1 - 2013 U6 - https://doi.org/10.3390/molecules18011314 SN - 1420-3049 VL - 18 IS - 1 SP - 1314 EP - 1324 PB - MDPI CY - Basel ER - TY - JOUR A1 - Javanainen, Matti A1 - Hammaren, Henrik A1 - Monticelli, Luca A1 - Jeon, Jae-Hyung A1 - Miettinen, Markus S. A1 - Martinez-Seara, Hector A1 - Metzler, Ralf A1 - Vattulainen, Ilpo T1 - Anomalous and normal diffusion of proteins and lipids in crowded lipid membranes JF - Faraday discussions N2 - Lateral diffusion plays a crucial role in numerous processes that take place in cell membranes, yet it is quite poorly understood in native membranes characterized by, e.g., domain formation and large concentration of proteins. In this article, we use atomistic and coarse-grained simulations to consider how packing of membranes and crowding with proteins affect the lateral dynamics of lipids and membrane proteins. We find that both packing and protein crowding have a profound effect on lateral diffusion, slowing it down. Anomalous diffusion is observed to be an inherent property in both protein-free and protein-rich membranes, and the time scales of anomalous diffusion and the exponent associated with anomalous diffusion are found to strongly depend on packing and crowding. Crowding with proteins also has a striking effect on the decay rate of dynamical correlations associated with lateral single-particle motion, as the transition from anomalous to normal diffusion is found to take place at macroscopic time scales: while in protein-poor conditions normal diffusion is typically observed in hundreds of nanoseconds, in protein-rich conditions the onset of normal diffusion is tens of microseconds, and in the most crowded systems as large as milliseconds. The computational challenge which results from these time scales is not easy to deal with, not even in coarse-grained simulations. We also briefly discuss the physical limits of protein motion. Our results suggest that protein concentration is anything but constant in the plane of cell membranes. Instead, it is strongly dependent on proteins' preference for aggregation. Y1 - 2013 U6 - https://doi.org/10.1039/c2fd20085f SN - 1359-6640 VL - 161 IS - 1 SP - 397 EP - 417 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Schnabel, Konrad A1 - Asendorpf, Jens B. T1 - Free associations as a measure of stable implicit attitudes JF - European journal of personality N2 - Two studies explored the psychometric properties of free association methods for the assessment of attitudes. Even though the stability of the actual associations was rather low, psychometric properties of the valence estimates of the free associations were highly satisfactory. Valence estimates of associations were provided by independent judges who rated the valence of the associations that were generated by participants. Valence estimates of the associations showed satisfactory internal consistencies and retest reliabilities over three weeks. Additionally, valence estimates of the associations were significantly and independently related to both explicit self-reported attitudes and implicit attitudes that were assessed with an OssiWessi Implicit Association Test. Free association methods represent a useful complement to the family of implicit measures and are especially suitable for the assessment of non-relative attitudes towards single attitude objects. KW - free associations KW - automatic associations KW - automatic attitudes KW - social cognition KW - implicit measures Y1 - 2013 U6 - https://doi.org/10.1002/per.1890 SN - 0890-2070 VL - 27 IS - 1 SP - 39 EP - 50 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Badalyan, Artavazd A1 - Neumann-Schaal, Meina A1 - Leimkühler, Silke A1 - Wollenberger, Ursula T1 - A Biosensor for aromatic aldehydes comprising the mediator dependent PaoABC-Aldehyde oxidoreductase JF - Electroanalysis : an international journal devoted to fundamental and practical aspects of electroanalysis N2 - A novel aldehyde oxidoreductase (PaoABC) from Escherichia coli was utilized for the development of an oxygen insensitive biosensor for benzaldehyde. The enzyme was immobilized in polyvinyl alcohol and currents were measured for aldehyde oxidation with different one and two electron mediators with the highest sensitivity for benzaldehyde in the presence of hexacyanoferrate(III). The benzaldehyde biosensor was optimized with respect to mediator concentration, enzyme loading and pH using potassium hexacyanoferrate(III). The linear measuring range is between 0.5200 mu M benzaldehyde. In correspondence with the substrate selectivity of the enzyme in solution the biosensor revealed a preference for aromatic aldehydes and less effective conversion of aliphatic aldehydes. The biosensor is oxygen independent, which is a particularly attractive feature for application. The biosensor can be applied to detect contaminations with benzaldehyde in solvents such as benzyl alcohol, where traces of benzaldehyde in benzyl alcohol down to 0.0042?% can be detected. KW - Aldehyde oxidoreductase KW - Benzaldehyde KW - Biosensor KW - Aromatic aldehydes KW - Molybdenum cofactor Y1 - 2013 U6 - https://doi.org/10.1002/elan.201200362 SN - 1040-0397 VL - 25 IS - 1 SP - 101 EP - 108 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Sliusarenko, O. Yu. A1 - Surkov, D. A. A1 - Gonchar, V. Yu. A1 - Chechkin, Aleksei V. T1 - Stationary states in bistable system driven by Levy noise JF - European physical journal special topics N2 - We study the properties of the probability density function (PDF) of a bistable system driven by heavy tailed white symmetric L,vy noise. The shape of the stationary PDF is found analytically for the particular case of the L,vy index alpha = 1 (Cauchy noise). For an arbitrary L,vy index we employ numerical methods based on the solution of the stochastic Langevin equation and space fractional kinetic equation. In contrast to the bistable system driven by Gaussian noise, in the L,vy case, the positions of maxima of the stationary PDF do not coincide with the positions of minima of the bistable potential. We provide a detailed study of the distance between the maxima and the minima as a function of the depth of the potential and the L,vy noise parameters. Y1 - 2013 U6 - https://doi.org/10.1140/epjst/e2013-01736-0 SN - 1951-6355 VL - 216 IS - 1 SP - 133 EP - 138 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - von Czapiewski, Marc A1 - Kreye, Oliver A1 - Mutlu, Hatice A1 - Meier, Michael A. R. T1 - Cross-metathesis versus palladium-catalyzed C-H activation acetoxy ester functionalization of unsaturated fatty acid methyl esters JF - European journal of lipid science and technology N2 - Two synthetic approaches to functionalize plant oil derived platform chemicals were investigated. For this purpose, methyl 10-undecenoate, which can be obtained by pyrolysis of castor oil, was used in olefin cross-metathesis under neat conditions forming an unsaturated a,?-acetoxy ester. A catalyst screening with 11 different ruthenium-based metathesis catalysts was performed, revealing that well-suited catalysts allow for full conversion and very good cross-metathesis selectivity at a loading of only 0.5?mol%. An alternative possibility to the aforementioned synthetic method is a palladium-catalyzed reaction of methyl 10-undecenoate with acetic acid in the presence of dimethyl sulfoxide. Here, the formation of linear and branched unsaturated acetoxy esters as well as a ketone was observed. The conversion as well as the selectivity of this procedure was studied under different reaction conditions and compared to the cross-metathesis results. Based on the successful functionalization of methyl 10-undecenoate, methyl oleate was investigated in this palladium-catalyzed C?H activation reaction. Due to the lower reactivity of the internal double bond the desired acetoxy ester was only obtained in moderate conversion in this case. In summary, this study clearly shows that palladium-catalyzed functionalization of unsaturated fatty compounds via C?H activation is an attractive alternative to the well-established olefin cross-metathesis procedure. KW - a KW - -Acetoxy esters KW - C?H oxidation KW - Cross-metathesis KW - Fatty acids KW - Pd catalysis Y1 - 2013 U6 - https://doi.org/10.1002/ejlt.201200196 SN - 1438-7697 VL - 115 IS - 1 SP - 76 EP - 85 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Herder, Martin A1 - Utecht, Manuel Martin A1 - Manicke, Nicole A1 - Grubert, Lutz A1 - Pätzel, Michael A1 - Saalfrank, Peter A1 - Hecht, Stefan T1 - Switching with orthogonal stimuli electrochemical ring-closure and photochemical ring-opening of bis(thiazolyl) maleimides JF - Chemical science N2 - The photochemistry as well as electrochemistry of novel donor-acceptor bis(morpholinothiazolyl)maleimides has been investigated. Proper substitution of these diarylethene-type molecular switches leads to the unique situation in which their ring-closure can only be accomplished electrochemically, while ring-opening can only be achieved photochemically. Hence, these switches operate with orthogonal stimuli, i.e. redox potential and light, respectively. The switch system could be optimized by introducing trifluoromethyl groups at the reactive carbon atoms in order to avoid by-product formation during oxidative ring closure. Both photochemical and electrochemical pathways were investigated for methylated, trifluoromethylated, and nonsymmetrical bis(morpholinothiazolyl) maleimides as well as the bis(morpholinothiazolyl) cyclopentene reference compound. With the aid of the nonsymmetrical "mixed" derivative, the mechanism of electrochemically driven ring closure could be elucidated and seems to proceed via a dicationic intermediate generated by two-fold oxidation. All experimental work has been complemented by density functional theory that provides detailed insights into the thermodynamics of the ring-open and closed forms, the nature of their excited states, and the reactivity of their neutral as well as ionized species in different electronic configurations. The particular diarylethene systems described herein could serve in multifunctional (logic) devices operated by different stimuli (inputs) and may pave the way to converting light into electrical energy via photoinduced "pumping" of redox-active meta-stable states. Y1 - 2013 U6 - https://doi.org/10.1039/c2sc21681g SN - 2041-6520 VL - 4 IS - 3 SP - 1028 EP - 1040 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Li, Hongguang A1 - Babu, Sukumaran Santhosh A1 - Turner, Sarah T. A1 - Neher, Dieter A1 - Hollamby, Martin J. A1 - Seki, Tomohiro A1 - Yagai, Shiki A1 - Deguchi, Yonekazu A1 - Möhwald, Helmuth A1 - Nakanishi, Takashi T1 - Alkylated-C-60 based soft materials regulation of self-assembly and optoelectronic properties by chain branching JF - Journal of materials chemistry : C, Materials for optical and electronic devices N2 - Derivatization of fullerene (C-60) with branched aliphatic chains softens C-60-based materials and enables the formation of thermotropic liquid crystals and room temperature nonvolatile liquids. This work demonstrates that by carefully tuning parameters such as type, number and substituent position of the branched chains, liquid crystalline C-60 materials with mesophase temperatures suited for photovoltaic cell fabrication and room temperature nonvolatile liquid fullerenes with tunable viscosity can be obtained. In particular, compound 1, with branched chains, exhibits a smectic liquid crystalline phase extending from 84 degrees C to room temperature. Analysis of bulk heterojunction (BHJ) organic solar cells with a ca. 100 nm active layer of compound 1 and poly(3-hexylthiophene) (P3HT) as an electron acceptor and an electron donor, respectively, reveals an improved performance (power conversion efficiency, PCE: 1.6 + 0.1%) in comparison with another compound, 10 (PCE: 0.5 + 0.1%). The latter, in contrast to 1, carries linear aliphatic chains and thus forms a highly ordered solid lamellar phase at room temperature. The solar cell performance of 1 blended with P3HT approaches that of PCBM/P3HT for the same active layer thickness. This indicates that C-60 derivatives bearing branched tails are a promising class of electron acceptors in soft (flexible) photovoltaic devices. Y1 - 2013 U6 - https://doi.org/10.1039/c3tc00066d SN - 2050-7526 VL - 1 IS - 10 SP - 1943 EP - 1951 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Tomczyk, Jaroslaw A1 - Sobolewska, Anna A1 - Nagy, Zsuzsanna T. A1 - Guillon, Daniel A1 - Donnio, Bertrand A1 - Stumpe, Joachim T1 - Photo- and thermal-processing of azobenzene-containing star-shaped liquid crystals JF - Journal of materials chemistry : C, Materials for optical and electronic devices N2 - A new class of star-shaped, liquid crystalline, low-molecular weight compounds functionalized with photochromic azobenzene and mesogenic groups was investigated in terms of light-induced anisotropy. The behaviour of the materials under the action of light with simultaneous or subsequent thermal treatment was examined with respect to the induction of anisotropy. The unconventional UV light treatment prior to the irradiation with linearly polarized light allowed induction of very high values of anisotropy (D = 0.77) at room temperature. Moreover, the simultaneous action of light and temperature led to the induction of higher values of dichroism in comparison with anisotropy generated by the standard procedure. Subsequent thermal treatment led to dewetting and the formation of 3D macroscopic stripe- and dome-like structures for one of the investigated compounds. Despite photoinduction of anisotropy by a single beam, the formation of polarization and surface relief gratings by two-beam interference pattern was also investigated. Y1 - 2013 U6 - https://doi.org/10.1039/c2tc00627h SN - 2050-7526 VL - 1 IS - 5 SP - 924 EP - 932 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Scheffler, Christiane T1 - Variable and invariable proportions in the ontogenesis of the human face JF - The journal of craniofacial surgery : an international journal dedicated to the practice of the art and science of craniofacial surgery ; official publication of the American Association of Pediatric Plastic Surgeons N2 - The human face shows individual features and features that are characteristic for sex and age (the loss of childlike characteristics during maturation). The analysis of facial dimensions is essential for identifying individual features also for forensic issues. The analysis of facial proportions was performed on photogrammetric data from front views of 125 children. The data were pooled from 2 different studies. The children's data were obtained from a longitudinal study and reduced by random generator to ensure the data of adults from a separate cross-sectional study. We applied principal component analysis on photogrammetric facial proportions of 169 individuals: 125 children (63 boys and 62 girls) aged 2-7 years and 44 adults (18 men and 26 women) aged 18-65 years. Facial proportions depend on age and sex. Three components described age: (1) proportions of facial height to head height, (2) proportions that involve endocanthal breadth, and (3) bigonial to bizygonial proportions. Proportions that associate with sex are connected with nasal distances and nasal to bizygonial distances. Twenty-three percent of the variance, particularly variance that are connected with proportions of lower and middle face heights to head height, do neither depend on sex nor on age and thus appear useful for screening purposes, eg, for dysmorphic genetic syndromes. KW - Human face KW - face proportions KW - ontogenesis KW - principal component analysis Y1 - 2013 U6 - https://doi.org/10.1097/SCS.0b013e31826d07a3 SN - 1049-2275 VL - 24 IS - 1 SP - 237 EP - 241 PB - Lippincott Williams & Wilkins CY - Philadelphia ER - TY - JOUR A1 - Barthold, Frauke Katrin A1 - Wiesmeier, Martin A1 - Breuer, L. A1 - Frede, Hans-Georg A1 - Wu, J. A1 - Blank, F. Benjamin T1 - Land use and climate control the spatial distribution of soil types in the grasslands of Inner Mongolia JF - Journal of arid environments N2 - The spatial distribution of soil types is controlled by a set of environmental factors such as climate, organisms, parent material and topography as well as time and space. A change of these factors will lead to a change in the spatial distribution of soil types. In this study, we use a digital soil mapping approach to improve our knowledge about major soil type distributing factors in the steppe regions of Inner Mongolia (China) which currently undergo tremendous environmental change, e.g. climate and land use change. We use Random Forests in an effort to map Reference Soil Groups according to the World Reference Base for Soil Resources (WRB) in the Xilin River catchment. We benefit from the superior prediction capabilities of RF and additional interpretive results in order to identify the major environmental factors that control spatial patterns of soil types. The nine WRB soil groups that were identified and spatially predicted for the study area are Arenosol, Calcisol, Cambisol, Chernozem, Cryosol, Gleysol, Kastanozem, Phaeozem and Regosol. Model and prediction performances of the RF model are high with an Out-of-Bag error of 51.6% for the model and a misclassification error for the predicted map of 28.9%. The main controlling factors of soil type distribution are land use, a set of topographic variables, geology and climate. However, land use and climate are of major importance and topography and geology are of minor importance. The visualizations of the predictions, the variable importance measures as result of RF and the comparisons of these with the spatial distribution of the environmental factors delivered additional, quantitative information of these controlling factors and revealed that intensively grazed areas are subjected to soil degradation. However, most of the area is still governed by natural soil forming processes which are driven by climate, topography and geology. Most importantly though, our study revealed that a shift towards warmer temperatures and lower precipitation regimes will lead to a change of the spatial distribution of RSGs towards steppe soils that store less carbon, i.e. a decrease of spatial extent of Phaeozems and an increase of spatial extent of Chernozems and Kastanozems. KW - Random Forests KW - Soil-environmental relationships KW - Steppe KW - Inner Mongolia KW - Land use change KW - Climate change Y1 - 2013 U6 - https://doi.org/10.1016/j.jaridenv.2012.08.004 SN - 0140-1963 VL - 88 IS - 1 SP - 194 EP - 205 PB - Elsevier CY - London ER -