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Under standard conditions the cross metathesis of allyl alcohols and methyl acrylate is accompanied by the formation of ketones, resulting from uncontrolled and undesired double bond isomerization. By conducting the CM in the presence of phenol, the catalyst loading and the reaction time required for quantiative conversion can be reduced, and isomerization can be suppressed. On the other hand, consecutive isomerization can be deliberately promoted by evaporating excess methyl acrylate after completing cross metathesis and by adding a base or silane as chemical triggers.
We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2− moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2− anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g∥ and g⊥, could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.
Intracellular photoactivation of caged cGMP induces myosin II and actin responses in motile cells
(2013)
Cyclic GMP (cGMP) is a ubiquitous second messenger in eukaryotic cells. It is assumed to regulate the association of myosin II with the cytoskeleton of motile cells. When cells of the social amoeba Dictyostelium discoideum are exposed to chemoattractants or to increased osmotic stress, intracellular cGMP levels rise, preceding the accumulation of myosin II in the cell cortex. To directly investigate the impact of intracellular cGMP on cytoskeletal dynamics in a living cell, we released cGMP inside the cell by laser-induced photo-cleavage of a caged precursor. With this approach, we could directly show in a live cell experiment that an increase in intracellular cGMP indeed induces myosin II to accumulate in the cortex. Unexpectedly, we observed for the first time that also the amount of filamentous actin in the cell cortex increases upon a rise in the cGMP concentration, independently of cAMP receptor activation and signaling. We discuss our results in the light of recent work on the cGMP signaling pathway and suggest possible links between cGMP signaling and the actin system.
With the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm of furylfulgides, these insights provide additional guidance to the rational design of photochemically switchable molecules.
The time-dependent approach to electronic spectroscopy, as popularized by Heller and coworkers in the 1980's, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption, emission and resonance Raman spectra of several diamondoids. Two-state models, the harmonic and the Condon approximations, are used for the calculations, making them easily applicable to larger molecules. The method is applied to nine pristine lower and higher diamondoids: adamantane, diamantane, triamantane, and three isomers each of tetramantane and pentamantane. We also consider a hybrid species “Dia = Dia” – a shorthand notation for a recently synthesized molecule comprising two diamantane units connected by a C[double bond, length as m-dash]C double bond. We resolve and interpret trends in optical and vibrational properties of these molecules as a function of their size, shape, and symmetry, as well as effects of “blending” with sp2-hybridized C-atoms. Time-dependent correlation functions facilitate the computations and shed light on the vibrational dynamics following electronic transitions.
We consider diffusion processes with a spatially varying diffusivity giving rise to anomalous diffusion. Such heterogeneous diffusion processes are analysed for the cases of exponential, power-law, and logarithmic dependencies of the diffusion coefficient on the particle position. Combining analytical approaches with stochastic simulations, we show that the functional form of the space-dependent diffusion coefficient and the initial conditions of the diffusing particles are vital for their statistical and ergodic properties. In all three cases a weak ergodicity breaking between the time and ensemble averaged mean squared displacements is observed. We also demonstrate a population splitting of the time averaged traces into fast and slow diffusers for the case of exponential variation of the diffusivity as well as a particle trapping in the case of the logarithmic diffusivity. Our analysis is complemented by the quantitative study of the space coverage, the diffusive spreading of the probability density, as well as the survival probability.
A Co(II)–imidazolate-4-amide-5-imidate based MOF, IFP-5, is synthesized by using an imidazolate anion-based novel ionic liquid as a linker precursor under solvothermal conditions. IFP-5 shows significant amounts of gas (N2, CO2, CH4 and H2) uptake capacities. IFP-5 exhibits an independent high spin Co(II) centre and antiferromagnetic coupling.
A rare example of in situ linker generation with the formation of soft porous Zn- and Co-MOFs (IFP-9 and -10, respectively) is reported. The flexible ethoxy groups of IFP-9 and -10 protrude into the 1D hexagonal channels. The gas-sorption behavior of both materials for H2, CO2 and CH4 showed wide hysteretic isotherms, typical for MOFs having a flexible substituent which can give rise to a gate effect.
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 ängstlich ‘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.
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.
Deep into the second half of the twentieth century the traditionalist definition of India as a country of villages remained dominant in official political rhetoric as well as cultural production. In the past two decades or so, this ruralist paradigm has been effectively superseded by a metropolitan imaginary in which the modern, globalised megacity increasingly functions as representative of India as a whole. Has the village, then, entirely vanished from the cultural imaginary in contemporary India? Addressing economic practices from upper-class consumerism to working-class family support strategies, this paper attempts to trace how ‘the village’ resurfaces or survives as a cultural reference point in the midst of the urban.
Filming illegals
(2013)
Introduction
(2013)
One of the central questions in psycholinguistic is understanding whether and how prosodic phrase boundaries are used to resolve syntactic ambiguities in sentence processing. The present work aimed to answer both, first, the effects of φ- and ι-boundaries on syntactic ambiguity resolution, and second, how the prosodic correlates of the auditory input are taken for the phonetic-phonology mapping in order to attain a meaningful sentence interpretation.
With regard to the first aim, we investigated locally syntactic ambiguities involving either φ- or ι-phrase boundaries in German and the structural preference that listeners have, based on the prosodic content. The experiments described in this work show that German listeners exploit both types of prosodic phrase boundaries to resolve local syntactic ambiguities, that however, their disambiguation altered by the presence or absence of prosodic cues correlated with the corresponding boundary. Specifically, the perception data revealed that the phonetically measured prosodic correlates of each prosodic boundary such as pitch accents, boundary tones, deaccentuation and durational properties do not contribute to ambiguity resolution in equal measure. Rather, it is the case that listeners rely primarily on prefinal lengthening as a correlate of phrasing in the vicinity of φ-phrase boundaries, while at the level of the ι-phrase boundary, boundary tones serve as phrasal cues. This way the results of the present work take account of the as yet missing information on individual contributions of prosodic correlates on listeners’ disambiguation of syntactically ambiguous sentences in German. It further implies that the question of how German listeners resolve syntactic ambiguities cannot simply be attributed to the presence or absence of prosodic correlates. The interpretation of the phrasal structure rather depends on a more general picture of cohesion between prosodic correlates and prosodic boundary sizes.
With respect to the second aim, the processing models proposed in the present work describe a specific phonetics-phonology mapping in the vicinity of both phrase boundaries. It is assumed that auditory sentence processing proceeds in several successively organized steps, during which listeners transform overt phonetic forms into language specific abstract surface forms. This process is referred to as phonetics-phonology mapping in the present work. Perceptual evidence resulting from the experiments of the present work suggest that the phonetics-phonology mapping is guided by the above mentioned boundary related prosodic correlates. The resulting abstract phonological structure is subjected to the syntax-prosody mapping, in turn. The outcome of the presented perception experiments are modulated in an Optimality-Theoretic framework. The offered OT-models are grounded on the assumption that single prosodic correlates are used by listeners as a signal to syntax in sentence processing. This is in line with studies arguing that the prosodic phrase structure determines the syntactic parse (Cutler et al., 1997; Warren et al., 1995; Pynte & Prieur, 1996; Snedeker & Trueswell, 2003; Kjelgaard & Speer, 1999), to name just a few.
Rhythm is a temporal and systematic organization of acoustic events in terms of prominence, timing and grouping, helping to structure our most basic experiences, such as body movement, music and speech. In speech, rhythm groups auditory events, e.g., sounds and pauses, together into words, making their boundaries acoustically prominent and aiding word segmentation and recognition by the hearer. After word recognition, the hearer is able to retrieve word meaning form his mental lexicon, integrating it with information from other linguistic domains, such as semantics, syntax and pragmatics, until comprehension is achieved. The importance of speech rhythm, however, is not restricted to word segmentation and recognition only. Beyond the word level rhythm continues to operate as an organization device, interacting with different linguistic domains, such as syntax and semantics, and grouping words into larger prosodic constituents, organized in a prosodic hierarchy. This dissertation investigates the function of speech rhythm as a sentence segmentation device during syntactic ambiguity processing, possible limitations on its use, i.e., in the context of second language processing, and its transferability as cognitive skill to the music domain.
Inhibition, attentional control, and causes of forgetting in working memory: a formal approach
(2013)
In many cognitive activities, the temporary maintenance and manipulation of mental objects is a necessary step in order to reach a cognitive goal. Working memory has been regarded as the process responsible for those cognitive activities. This thesis addresses the question: what limits working-memory capacity (WMC)? A question that still remains controversial (Barrouillet & Camos, 2009; Lewandowsky, Oberauer, & Brown, 2009). This study attempted to answer this question by proposing that the dynamics between the causes of forgetting and the processes helping the maintenance, and the manipulation of the memoranda are the key aspects in understanding the limits of WMC.
Chapter 1 introduced key constructs and the strategy to examine the dynamics between inhibition, attentional control, and the causes of forgetting in working memory.
The study in Chapter 2 tested the performance of children, young adults, and old adults in a working-memory updating-task with two conditions: one condition included go steps and the other condition included go, and no-go steps. The interference model (IM; Oberauer & Kliegl, 2006), a model proposing interference-related mechanisms as the main cause of forgetting was used to simultaneously fit the data of these age groups. In addition to the interference-related parameters reflecting interference by feature overwriting and interference by confusion, and in addition to the parameters reflecting the speed of processing, the study included a new parameter that captured the time for switching between go steps and no-go steps. The study indicated that children and young adults were less susceptible than old adults to interference by feature overwriting; children were the most susceptible to interference by confusion, followed by old adults and then by young adults; young adults presented the higher rate of processing, followed by children and then by old adults; and young adults were the fastest group switching from go steps to no-go steps.
Chapter 3 examined the dynamics between causes of forgetting and the inhibition of a prepotent response in the context of three formal models of the limits of WMC: A resources model, a decay-based model, and three versions of the IM. The resources model was built on the assumption that a limited and shared source of activation for the maintenance and manipulation of the objects underlies the limits of WMC. The decay model assumes that memory traces of the working-memory objects decay over time if they are not reactivated via different mechanisms of maintenance. The IM, already described, proposes that interference-related mechanisms explain the limits of WMC. In two experiments and in a reanalysis of data of the second experiment, one version of the IM received more statistical support from the data. This version of the IM proposes that interference by feature overwriting and interference by confusion are the main factors underlying the limits of WMC. In addition, the model suggests that experimental conditions involving the inhibition of a prepotent response reduce the speed of processing and promotes the involuntary activation of irrelevant information in working memory.
Chapter 4 summed up Chapter 2 and 3 and discussed their findings and presented how this thesis has provided evidence of interference-related mechanisms as the main cause of forgetting, and it has attempted to clarify the role of inhibition and attentional control in working memory. With the implementation of formal models and experimental manipulations in the framework of nonlinear mixed models the data offered explanations of causes of forgetting and the role of inhibition in WMC at different levels: developmental effects, aging effects, effects related to experimental manipulations and individual differences in these effects. Thus, the present approach afforded a comprehensive view of a large number of factors limiting WMC.
This dissertation is about factors that contribute to the surface forms of tones in connected speech in Akan. Akan is an African tone language, which is spoken in Ghana. It has two level tones (low and high), automatic and non-automatic downstep. Downstep is the major factor that influences the surface forms of tones. The thesis shows that downstep is caused by declination. It is argued that declination is an intonational property of Akan, which serves to signal coherence. A phonological representation using a high and a low register tone, associating to the left and right edge of an intonational phrase (IP), respectively, is proposed. Declination/downstep is modelled using a (phonetic) pitch implementation algorithm (Liberman & Pierrehumbert, 1984). An innovative application of the algorithm is presented, which naturally captures the relation between declination and downstep in Akan. Another important factor is the prosodic manifestation of sentence level pragmatic meanings, such as sentence mode and focus. Regarding the former, the thesis shows that a post-lexical low tone, which associates with the right edge of an IP, signals interrogativity. Additionally, lexical tones in Yes – No questions are realized in a higher pitch register, which does not lead to a reduction of declination. It is claimed that the higher register is not part of the phonological representation in Akan, but that it emerges at the phonetic level to compensate for the ‘unnatural’ form of the question morpheme and to satisfy the Frequency code (Gussenhoven, 2002; 2004). An extension of Rialland’s (2007) typology in terms of a new category called “low tense” question prosody is proposed. Concerning focus marking, it is argued that the use of the morpho-syntactic focus marking strategy is related to extra grammatical factors, such as hearer expectation, discourse expectability (Zimmermann, 2007) and emphasis (Hartmann, 2008). If a speaker of Akan wants to highlight a particular element in a sentence, in-situ, i.e. by means of prosody, the default prosodic structure is modified in such a way that the focused element forms its own phonological phrase (pP). If it is already contained in a pP, the boundary deliminating the focused element is enhanced (Féry, 2012). This restructuring/enhancement is accompanied by an interruption of the otherwise continuous melody due to insertion of a pause and/or a glottal stop. Beside declination and intonation, raising of H tones applies in Akan. H raising is analyzed as a local anticipatory planning effect, employed at the phonetic level, which enhances the perceptual distance between low and high tones. Low tones are raised, if they are wedged between two high tones. L raising is argued to be a local carryover effect (co-articulation). Further, it is demonstrated that global anticipatory raising takes place. It is shown that Akan speakers anticipate the length of an IP. Preplanning (anticipatory raising) is argued to be an important process at the level of pitch implementation. It serves to ensure that declination can be maintained throughout the IP, which prevents pitch resetting.
The melody of an Akan sentence is largely determined by the choice of words. The inventory of post-lexical tones is small. It consists of post-lexical register tones, which trigger declination and post-lexical intonational tones, which signal sentence type. The overall melodic shape is falling. At the local level, H raising and L raising occur. At the global level, initial low and high tones are realized higher if they occur in a long and/or complex sentence. This dissertation shows that many factors, which emerge at different levels of the tone production process, contribute to the surface form of tones in Akan.