Sulfation patterns of glycosaminoglycans (GAG) govern the electrostatic complexation of biomolecules and thus allow for modulating the release profiles of growth factors from GAG-based hydrogels. To explore options related to this, selectively desulfated heparin derivatives were prepared, thoroughly characterized, and covalently converted with star-shaped poly(ethylene glycol) into binary polymer networks. The impact of the GAG sulfation pattern on the network characteristics of the obtained hydrogels was theoretically evaluated by mean field methods and experimentally analyzed by rheometry and swelling measurements. Sulfation-dependent differences of reactivity and miscibility of the heparin derivatives were shown to determine network formation. A theory-based design concept for customizing growth factor affinity and physical characteristics was introduced and validated by quantifying the release of fibroblast growth factor 2 from a set of biohybrid gels. The resulting new class of cell-instructive polymer matrices with tunable GAG sulfation will be instrumental for multiple applications in biotechnology and medicine.
Using a variant of the Bond Fluctuation Model which improves its parallel efficiency in particular running on graphic cards we perform large scale simulations of polymer brushes in poor explicit solvent. Grafting density, solvent quality, and chain length are varied. Different morphological structures in particular octopus micelles are observed for low grafting densities. We reconsider the theoretical model for octopus micelles proposed by Williams using scaling arguments with the relevant scaling variable being ?/?(c), and with the characteristic grafting density given by ?(c) ~ N(-4/3). We find that octopus micelles only grow laterally, but not in height and we propose an extension of the model by assuming a cylindrical shape instead of a spherical geometry for the micelle-core. We show that the scaling variable ?/?(c) can be applied to master plots for the averaged height of the brush, the size of the micelles, and the number of chains per micelle. The exponents in the corresponding power law relations for the grafting density and chain length are in agreement with the model for flat cylindrical micelles. We also investigate the surface roughness and find that polymer brushes in explicit poor solvent at grafting densities higher than the stretching transition are flat and surface rippling can only be observed close to the stretching transition.
Unravelling details of charge, structure and molecular interactions of functional polymer coatings defines an important analytical challenge that requires the extension of current methodologies. In this article we demonstrate how streaming current measurements interpreted with combined self consistent field (SCF) and soft surface electrokinetic theories allow the evaluation of the segment distribution within poly(ethylene oxide) (PEO) brushes beyond the resolution limits of neutron reflectivity technique.
We perform Monte-Carlo simulations of a binary, strongly separated mixture of A- and B-type homopolymers with some amount of random AB copolymers added. The interface is analyzed and the interface tension is calculated using the model of capillary waves. We can clearly demonstrate that random copolymers are localized at real, fluctuating interfaces between incompatible polymer species and micellization is not favored over adsorption. Our study proves that random copolymers are potential candidates for compatibilization of polymer-polymer mixtures. By simulating random copolymers in a one-component bulk and comparing their free energy to the copolymers adsorbed at the two-phase interface we show that the adsorption is thermodynamically stable. We use scaling arguments developed for ideal and non-fluctuating interfaces to rationalize the simulation results and we calculate the reduction of interface tension with increasing amount of the adsorbed copolymers.
We studied the formation of hydrogen-bonded supramolecular polymers of Ethyl Hexyl Urea Toluene (EHUT) on a gold (111) surface by low temperature scanning tunneling microscopy. Tunneling spectroscopy performed along an individual molecule embedded in a self-assembled layer revealed strong changes in the value of the HOMO-LUMO gap. A variation of the LUMO state is attributed to the effect of space charge accumulation resulting from anisotropic adhesion of the molecule. In addition, for specific tunneling conditions, changes induced through the formation of hydrogen bonds became visible in the differential conductance (dI/dV) maps; isolated molecules, hydrogen bonded dimers and supramolecular polymers of EHUT were distinguishable through their electronic properties.
Polymer chains form lamellar structures during crystallization which display a memory of thermal history. Using molecular dynamics simulations and primitive path analysis, we show a direct dependence of both density and crystalline stem length on the local entanglement length. The slow relaxation of the entanglement state after a change of external conditions can directly explain the role of thermal history for polymer crystallization, in particular memory effects. The analysis of the local entanglement state can be used to predict the occurrence of nucleation events. Our results present a fresh insight of the nonequilibrium properties of polymer crystals which might be identified as "frozen topology" of polymer melts.
Ego disturbances in schizophrenia might be caused by a failure of the efference copy mechanism, which compares efferent with reafferent signals and attenuates the sensory consequences of self-produced movements. We carried out a functional magnetic resonance imaging study in which 16 patients with schizophrenia and 16 healthy matched controls were studied while performing both intentional and unintentional continuous hand movements in two consecutive experiments. We periodically varied the delay of visual feedback to create a sensory-motor discrepancy. Exclusively for intentional movements the activation pattern of the inferior frontal gyrus (IFG) in patients was opposite to that of controls: less attenuated during time-congruent feedback and less activated during time-incongruent feedback. Additionally, several functional connections within the mismatch detection network (IFG with insula, putamen, medial orbitofrontal cortex) were affected. Also, activity of the dysconnected orbitofrontal cortex was correlated with ego disturbance in patients. We discuss that in healthy individuals the IFG might enable a distinction between self and non-self using time-characteristics of feedback, whereas in patients this sensory mismatch detection appears to be altered. Moreover, due to the dysconnectivity of the IFG, the efferent and reafferent signal exchange between perceptual and motor areas seems to be affected. This might cause self-monitoring deficits in patients, phenomena that contribute to the emergence of ego disturbances.
Molecular dynamics simulations are applied to investigate salt-free planar polyelectrolyte brushes under poor solvent conditions. Starting above the ?-point with a homogeneous brush and then gradually reducing the temperature, the polymers initially display a lateral structure formation, forming vertical bundles of chains. A further reduction of the temperature (or solvent quality) leads to a vertical collapse of the brush. By varying the size and selectivity of the counterions, we show that lateral structure formation persists and therefore demonstrate that the entropy of counterions being the dominant factor for the formation of the bundle phase. By applying an external compression force on the brush we calculate the minimal work done on the polymer phase only and prove that the entropy gain of counterions in the bundle state, as compared to the homogeneously collapsed state at the same temperature, is responsible for the lateral microphase segregation. As a consequence, the observed lateral structure formation has to be regarded universal for osmotic polymer brushes below the ?-point.
When two dissimilar stimuli are presented to the eyes, perception alternates between multiple interpretations, a phenomenon dubbed binocular rivalry. Numerous recent imaging studies have attempted to unveil neural substrates underlying multistable perception. However, these studies had a conceptual constraint: access to observers' perceptual state relied on their introspection and active report. Here, we investigated to what extent neural correlates of binocular rivalry in healthy humans are confounded by this subjective measure and by action. We used the optokinetic nystagmus and pupil size to objectively and continuously map perceptual alternations for binocular-rivalry stimuli. Combining these two measures with fMRI allowed us to assess the neural correlates of binocular rivalry time locked to the perceptual alternations in the absence of active report. When observers were asked to actively report their percept, our objective measures matched the report. In this active condition, objective measures and subjective reporting revealed that occipital, parietal, and frontal areas underlie the processing of binocular rivalry, replicating earlier findings. Furthermore, objective measures provided additional statistical power due to their continuous nature. Importantly, when observers passively experienced rivalry without reporting perceptual alternations, a different picture emerged: differential neural activity in frontal areas was absent, whereas activation in occipital and parietal regions persisted. Our results question the popular view of a driving role of frontal areas in the initiation of perceptual alternations during binocular rivalry. Instead, we conclude that frontal areas are associated with active report and introspection rather than with rivalry per se.
The existence of a free energy barrier, which prohibits the upward motion of retracted molecules into the surface region of starlike polymer brushes, is analyzed through molecular dynamics simulations in good solvent. This barrier emerges at moderate and high grafting densities, as a result of a density-discontinuity at the branching points of the highly stretched starlike molecules. The vertical force profiles of brushes of varying densities are taken with the help of a probe-particle that is gradually moved into the brush, and the results are compared with the density profiles and their negative gradients which generate the local osmotic pressures. Chain expulsion simulations, supported by scaling theory, are conducted to understand the dynamics of individual molecules inside the brushes. We prove that the flip-rates between retracted and extended states, being of relevance for the generation of efficiently switchable, environment-responsive brush layers, are determined by the elastic tension of the stretched molecules.
Using molecular dynamics simulations, we study the properties of liquid state polymer-nanoparticle composites confined between two parallel substrates, with an attractive polymer-substrate interaction. Polymers are in the semidilute regime at concentrations far above the overlap point, and nanoparticles are in good solvent and without enthalpic attraction to the substrates. An increase of temperature then triggers the crystallization of nanoparticles on one of the two substrate surfaces-a surprising phenomenon, which is explained in terms of scaling theory, such as through competing effects of adsorption-and correlation blobs. Moreover, we show that the first, closely packed layer of nanoparticles on the substrate increases the depletion attraction of additional nanoparticles from the bulk, thereby enhancing and stabilizing the formation of a crystalline phase on the substrate. Within the time frame accessible to our numerical simulations, the crystallization of nanoparticles was irreversible; that is, their crystalline phase, once created, remained undamaged after a decrease of the temperature. Our study leads to a class of thermoreactive nanomaterials, in which the transition between a homogeneous state with dissolved nanoparticles and a surface-crystallized state is triggered by a temperature jump.
Genome-wide association studies have identified the CACNA1C single nucleotide polymorphism (SNP) rs1006737 as one of the most consistent genetic findings as susceptibility locus for major psychiatric disorders. Furthermore, animal and genetic imaging studies have reported strong functional evidence for the association of CACNA1C with learning, memory, neural plasticity, and its association with the hippocampal formation. In the present study we investigated the impact of the CACNA1C SNP rs1006737 on the fractional anisotropy (FA) in the hippocampal formation as well as on verbal learning and memory in healthy individuals.
Pain catastrophizing, an excessively negative cognitive and emotional orientation toward pain, is one of the most important psychological determinants of the individual pain experience. The neural basis of the association between catastrophizing and enhanced pain perception is only incompletely understood. Recently, several forms of pain modulation by cognitive and emotional factors have been found to at least partly rely on descending pain modulatory pathways that govern spinal gating mechanisms. We used the spinally mediated nociceptive flexor reflex (RIII reflex) to investigate whether spinal nociceptive transmission is affected when participants engage in catastrophizing self-statements.
We use the bond fluctuation model with explicit solvent to study single polymer chains under poor solvent conditions. Static and dynamic properties of the bond fluctuation model with explicit solvent are compared with the implicit solvent model, and the ?-temperatures are determined for both solvent models. We show that even in the very poor solvent regime, dynamics is not frozen for the explicit solvent model. We investigate some aspects of the structure of a single collapsed globule and show that rather large chain lengths are necessary to reach the scaling regime of a dense sphere. The force-extension curve of a single polymer chain under poor solvent conditions in the fixed end-to-end distance ensemble is analyzed. We find that the transition of the tadpole conformation to the stretched chain conformation is rather smooth because of fluctuation effects, which is in agreement with recent experimental results.
The most frequently used method for fiber tractography based on diffusion tensor imaging (DTI) is associated with restrictions in the resolution of crossing or kissing fibers and in the vicinity of tumor or edema. Tractography based on high-angular-resolution diffusion imaging (HARDI) is capable of overcoming this restriction. With compressed sensing (CS) techniques, HARDI acquisitions with a smaller number of directional measurements can be used, thus enabling the use of HARDI-based fiber tractography in clinical practice.
The mechanisms underlying hemispheric specialization of memory are not completely understood. Functional magnetic resonance imaging (fMRI) can be used to develop and test models of hemispheric specialization. In particular for memory tasks however, the interpretation of fMRI results is often hampered by the low reliability of the data. In the present study we therefore analyzed the test-retest reliability of fMRI brain activation related to an implicit memory encoding task, with a particular focus on brain activity of the medial temporal lobe (MTL). Fifteen healthy subjects were scanned with fMRI on two sessions (average retest interval 35?days) using a commonly applied novelty encoding paradigm contrasting known and unknown stimuli. To assess brain lateralization, we used three different stimuli classes that differed in their verbalizability (words, scenes, fractals). Test-retest reliability of fMRI brain activation was assessed by an intraclass-correlation coefficient (ICC), describing the stability of inter-individual differences in the brain activation magnitude over time. We found as expected a left-lateralized brain activation network for the words paradigm, a bilateral network for the scenes paradigm, and predominantly right-hemispheric brain activation for the fractals paradigm. Although these networks were consistently activated in both sessions on the group level, across-subject reliabilities were only poor to fair (ICCs???0.45). Overall, the highest ICC values were obtained for the scenes paradigm, but only in strongly activated brain regions. In particular the reliability of brain activity of the MTL was poor for all paradigms. In conclusion, for novelty encoding paradigms the interpretation of fMRI results on a single subject level is hampered by its low reliability. More studies are needed to optimize the retest reliability of fMRI activation for memory tasks.
The suitability of different gelling agents as MRI phantoms was evaluated in terms of homogeneity, gel stability and reproducibility. Time and effort for preparation were also taken into account. The relaxation times of various gel compositions were estimated. Carbomer-980 and Carbopol-974P were determined to be promising novel phantom materials. These gelling agents are readily available, inexpensive and easy to handle given that thermal treatment is not required. Furthermore, the viscoelasticity of their polymer network is pH-dependent. With such characteristics, it was even possible to embed sensitive objects and retrieve them after testing. This was demonstrated with a fiber phantom for Diffusion Weighted MRI applications. Since Carbomer-980 and Carbopol-974P are non-hazardous, they are also suitable for multimodal setups (e.g., MRI as well as ultrasonic imaging).
Up to now, fiber tractography in the clinical routine is mostly based on diffusion tensor imaging (DTI). However, there are known drawbacks in the resolution of crossing or kissing fibers and in the vicinity of a tumor or edema. These restrictions can be overcome by tractography based on High Angular Resolution Diffusion Imaging (HARDI) which in turn requires larger numbers of gradients resulting in longer acquisition times. Using compressed sensing (CS) techniques, HARDI signals can be obtained by using less non-collinear diffusion gradients, thus enabling the use of HARDI-based fiber tractography in the clinical routine.
Theory of Mind (ToM) is the ability to infer other peoples mental states like intentions or desires. ToM can be differentiated into affective (i.e., recognizing the feelings of another person) and cognitive (i.e., inferring the mental state of the counterpart) subcomponents. Recently, subcortical structures such as the basal ganglia (BG) have also been ascribed to the multifaceted concept ToM and most BG disorders have been reported to elicit ToM deficits. In order to assess both the correlates of affective and cognitive ToM as well as involvement of the basal ganglia, 30 healthy participants underwent event-related fMRI scanning, neuropsychological testing, and filled in questionnaires concerning different aspects of ToM and empathy. Directly contrasting affective (aff) as well as cognitive (cog) ToM to the control (phy) condition, activation was found in classical ToM regions, namely parts of the temporal lobe including the superior temporal sulcus, the supplementary motor area, and parietal structures in the right hemisphere. The contrast aff > phy yielded additional activation in the orbitofrontal cortex on the right and the cingulate cortex, the precentral and inferior frontal gyrus and the cerebellum on the left. The right BG were recruited in this contrast as well. The direct contrast aff > cog showed activation in the temporoparietal junction and the cingulate cortex on the right as well as in the left supplementary motor area. The reverse contrast cog > aff however did not yield any significant clusters. In summary, affective and cognitive ToM partly share neural correlates but can also be differentiated anatomically. Furthermore, the BG are involved in affective ToM and thus their contribution is discussed as possibly providing a motor component of simulation processes, particularly in affective ToM.
Functional magnetic resonance imaging (fMRI) can be combined with genotype assessment to identify brain systems that mediate genetic vulnerability to mental disorders ("imaging genetics"). A data analysis approach that is widely applied is "functional connectivity". In this approach, the temporal correlation between the fMRI signal from a pre-defined brain region (the so-called "seed point") and other brain voxels is determined. In this technical note, we show how the choice of freely selectable data analysis parameters strongly influences the assessment of the genetic modulation of connectivity features. In our data analysis we exemplarily focus on three methodological parameters: (i) seed voxel selection, (ii) noise reduction algorithms, and (iii) use of additional second level covariates. Our results show that even small variations in the implementation of a functional connectivity analysis can have an impact on the connectivity pattern that is as strong as the potential modulation by genetic allele variants. Some effects of genetic variation can only be found for one specific implementation of the connectivity analysis. A reoccurring difficulty in the field of psychiatric genetics is the non-replication of initially promising findings, partly caused by the small effects of single genes. The replication of imaging genetic results is therefore crucial for the long-term assessment of genetic effects on neural connectivity parameters. For a meaningful comparison of imaging genetics studies however, it is therefore necessary to provide more details on specific methodological parameters (e.g., seed voxel distribution) and to give information how robust effects are across the choice of methodological parameters.
Genome-wide association studies identified the single nucleotide polymorphism rs1344706 in ZNF804A as a common risk-variant for schizophrenia and bipolar disorder. Whereas the molecular function of ZNF804A is yet unclear, recent imaging genetics studies have started to characterize the neural systems architecture linking rs1344706 genotype to psychosis. Carring rs1344706 risk-alleles was associated with a decrease in functional connectivity within the dorsolateral prefrontal cortices (DLPFCs) as well as an increase in connectivity between the DLPFC and the hippocampal formation (HF) in the context of a working memory task. The present study aimed at replicating these findings in an independent sample of 94 healthy subjects. Subjects were genotyped for rs1344706 and performed a working memory task during functional magnetic resonance imaging. Results indicate no support for a decrease of functional coupling between the bilateral DLPFCs at higher ZNF804A risk status. However, the current data show the previously described alteration in functional coupling between the right DLPFC and the HFs, albeit with weaker effects. Decoupled by default, the functional connectivity between the right DLPFC and anterior HFs increased with the number of rs1344706 risk alleles. The present data support fronto-hippocampal dysconnectivity as intermediate phenotype linking rs1344706 genotype to psychosis. We discuss the issues in replicating the interhemispheric DLPFC coupling in light of the effect sizes rs1344706 genotype has on brain function, concluding that further independent replication studies are fundamentally needed to ascertain the role of rs1344706 in the functional integration of neural systems.
We study the effective interactions between nanoparticles immersed in an athermal polymer solution using Molecular dynamics. The directly measured polymer-induced depletion forces are well described with a scaling model in which the attraction between particles is caused by the depletion of concentration blobs and thus independent of the length of the polymer chains. We find strong evidence for a repulsive barrier which arises when the distance between the particles is of the order of the correlation length of the solution and which can be interpreted as a packing effect of concentration blobs. Interestingly, the scaling picture can be extended into the regime in which higher virial coefficients of the polymer solution become relevant. We derive a universal relation between the attraction force at the particle contact, f(0), and the osmotic pressure ? as f(0)??(2/3), demonstrating its validity over a wide range of concentrations of the polymer solution.
We study the segregation of two long chains from parallel but randomly twisted start conformations under good solvent conditions using Monte Carlo simulations to mimic chromatin segregation after replication in eukaryotic cells in the end of prophase. To measure the segregation process, we consider the center-of-mass separation between the two chains and the average square distance between the monomers which were connected before segregation starts. We argue that segregation is dominated by free diffusion of the chains, assuming that untwisting can be achieved by Rouse-like fluctuations on the length scale of a twisted loop. Using scaling analysis, we find that chain dynamics is in very good agreement with the free diffusion hypothesis, and segregation dynamics follows this scaling nearly. Long chains, however, show retardation effects that can be described by a new (to us) dynamical exponent, which is slightly larger than the dynamical exponent for Rouse-like diffusion. Our results indicate that nearly free diffusion of chains during a timescale of a few Rouse-times can lead to segregation of chains. A main obstacle during segregation by free diffusion is random twists between daughter strands. We have calculated the number of twists formed by the daughter strands in the start conformations, which turns out to be rather low and increases only with the square-root of the chain length.
People vicariously experience embarrassment when observing others public pratfalls or etiquette violations. In two consecutive studies we investigated the subjective experience and the neural correlates of vicarious embarrassment for others in a broad range of situations. We demonstrated, first, that vicarious embarrassment was experienced regardless of whether the observed protagonist acted accidentally or intentionally and was aware or unaware that he/she was in an embarrassing situation. Second, using functional magnetic resonance imaging (fMRI), we showed that the anterior cingulate cortex and the left anterior insula, two cortical structures typically involved in vicarious feelings of others pain, are also strongly implicated in experiencing the social pain for others flaws and pratfalls. This holds true even for situations that engage protagonists not aware of their current predicament. Importantly, the activity in the anterior cingulate cortex and the left anterior insula positively correlated with individual differences in trait empathy. The present findings establish the empathic process as a fundamental prerequisite for vicarious embarrassment experiences, thus connecting affect and cognition to interpersonal processes."When we are living with people who have a delicate sense of propriety, we are in misery on their account when anything unbecoming is committed. So I always feel for and with Charlotte when a person is tipping his chair. She cannot endure it." [Elective Affinities, J. W. Goethe].
Distraction from pain reduces pain perception, and imaging studies have suggested that this may at least partially be mediated by activation of descending pain inhibitory systems. Here, we used the nociceptive flexor reflex (RIII reflex) to directly quantify the effects of different distraction strategies on basal spinal nociception and its temporal summation. Twenty-seven healthy subjects participated in 3 distraction tasks (mental imagery, listening to preferred music, spatial discrimination of brush stimuli) and, in a fourth task, concentrated on the painful stimulus. Results show that all 3 distraction tasks reduced pain perception, but only the brush task also reduced the RIII reflex. The concentration-on-pain task increased both pain perception and the RIII reflex. The extent of temporal summation of pain perception and the extent of temporal summation of the RIII reflex were not affected by any of the tasks. These results suggest that some, but not all, forms of pain reduction by distraction rely on descending pain inhibition. In addition, pain reduction by distraction seems to preferentially affect mechanisms of basal nociceptive transmission, not of temporal summation.
The cross-linking of polymer brushes is studied using the bond-fluctuation model. By mapping the cross-linking process into a two-dimensional (2D) percolation problem within the lattice of grafting points, we investigate the gelation transition in detail. We show that the particular properties of cross-linked polymer brushes can be reduced to the distribution of bonds which are formed between the grafted chains, and we propose scaling arguments to relate the gelation threshold to the chain length and the grafting density. The gelation threshold is lower than the percolation threshold for 2D bond percolation because of the longer range and broad distribution of bonds formed by the cross-linking process. We term this type of percolation problem star percolation. We observe a broad crossover from mean-field to critical percolation behavior by analyzing the cluster size distribution near the gelation threshold.
We investigated membrane-like polymer structures of fractal connectivity such as Sierpinski gaskets and Sierpinski carpets applying the bond fluctuation model in three dimensions. Without excluded volume (phantom), both polymeric fractals obey Gaussian elasticity on larger scales determined by their spectral dimension. On the other hand, the swelling effect due to excluded volume is rather distinct between the two polymeric fractals: Self-avoiding Sierpinski gaskets can be described using a Flory-type mean-field argument. Sierpinski carpets having a spectral dimension closer to perfect membranes are significantly more strongly swollen than predicted. Based on our simulation results it cannot be excluded that Sierpinski carpets in athermal solvent show a flat phase on larger scales. We tested the self-consistency of Flory predictions using a virial expansion to higher orders. From this we conclude that the third virial coefficient contributes marginally to Sierpinski gaskets, but higher order virial coefficients are relevant for Sierpinski carpets.
A tight link between linguistic functions and activation of motor areas has been consistently reported, indicating that the 2 systems share functional neural resources. Few efforts have been made to explore whether this knowledge could aid the rehabilitation of aphasia.
A "walking" process of Ni catalysts during Kumada catalyst-transfer polycondensation along polymerizing poly(3-hexylthiophene), P3HT, chains was investigated. To simplify polymer end group identifications, a compound Br-C(6)H(4)-Ni(dppe)-Br was prepared and used as an externally addable initiator. Normally, aryl moieties present in initiators incorporate into the structure of the resulting P3HT as the starting groups. We demonstrate that due to the presence of the C-Br group located in the para-position to the Ni substituent of the initiator, two different polymeric products are formed. One of them is the "normal" product, that is, P3HT with a para-bromophenyl end group, whereas another one has the phenyl ring inside the P3HT chain. The content of the product with the internal phenyl ring increases with the increase of the polymerization degree. Control experiments demonstrated that no intermolecular catalyst transfer takes place in the conditions used. Such results suggest that catalytic Ni(0) species are able to walk along the polymerizing chain containing many tens of thienyl rings up to the opposite end and can initiate polymerization there. Numerical analysis of a random hopping model was undertaken, which revealed that a combination of a random catalyst walking along the chain and a "sticking effect" at the end groups is operative in Kumada catalyst-transfer polycondensation.
The coexistence of melting and growth during heating is observed by molecular dynamics simulations of semicrystalline entangled polymers. During heating, some microcrystalline domains (MCDs) are melted while others are still growing, which can be associated with multiple-peaked melting endotherms. The growth of MCDs stability is related to the increase of molecular disorder. The increasing of the stem length during annealing close to the melting point is contributed by the orientational correlation in the semimelted surface regions while direct trans-trans states are decreasing which increases the flexibility and mobility of the crystalline stems.
The medial temporal lobe (MTL) is essential for declarative memory formation, but also a frequent source of seizures. To decrease the risk of amnestic impairments after temporal lobectomy, functional magnetic resonance imaging (fMRI) is increasingly used to establish pre-operative measures for a prognosis of postoperative memory performance. The present study addresses one of the major challenges in clinical fMRI, the interpretation of activation pattern in single subjects. Before investigating patients however, it must be first assessed to which extent the verbal memory paradigm can be used to determine the lateralization and the functional neuroanatomy of MTL-activity. Therefore, this study took a "step backwards" by first examining healthy subjects without known MTL pathology.
Mixed polymer brushes as functional ultra thin films for surface functionalization have an enormous potential to create a variety of smart, switchable, and multifunctional surfaces and thin films. It is shown how computer simulations can contribute to a better understanding of the switching behavior of brushes. Furthermore, it is described how polymer brushes can be used to create surfaces with switchable ultrahydrophobicity and wettability gradients, as well as functional layers for the immobilization of nanoparticles. Applications of these versatile and multifunctional brush coatings are envisioned in many areas including fluid control, microfluidics, and thin film sensors.
Via computer simulations, we demonstrate how a densely grafted layer of polymers, a brush, could be turned into an efficient switch through chemical modification of some of its end monomers. In this way, a surface coating with reversibly switchable properties can be constructed. We analyze the fundamental physical principle behind its function, a recently discovered surface instability, and demonstrate that the combination of a high grafting density, an inflated end-group size, and a high degree of monodispersity is a condition for an optimal functionality of the switch.
Monte Carlo simulations using the bond fluctuation method with explicit solvent reveal the mechanism of enhanced permeability of lipid bilayers induced by the adsorption of nanoparticles with controlled hydrophobicity. Simulation results indicate an adsorption transition of nanoparticles on the bilayer in a certain range of relative degree of hydrophobicity. In this range the nanoparticles can translocate through the bilayer, reversibly destabilizing the structure of the bilayer and inducing enhanced permeability for water and small solutes. This transition is broader for amphiphilic nanoparticles.
Automated gray matter segmentation of magnetic resonance imaging data is essential for morphometric analyses of the brain, particularly when large sample sizes are investigated. However, although detection of small structural brain differences may fundamentally depend on the method used, both accuracy and reliability of different automated segmentation algorithms have rarely been compared. Here, performance of the segmentation algorithms provided by SPM8, VBM8, FSL and FreeSurfer was quantified on simulated and real magnetic resonance imaging data. First, accuracy was assessed by comparing segmentations of twenty simulated and 18 real T1 images with corresponding ground truth images. Second, reliability was determined in ten T1 images from the same subject and in ten T1 images of different subjects scanned twice. Third, the impact of preprocessing steps on segmentation accuracy was investigated. VBM8 showed a very high accuracy and a very high reliability. FSL achieved the highest accuracy but demonstrated poor reliability and FreeSurfer showed the lowest accuracy, but high reliability. An universally valid recommendation on how to implement morphometric analyses is not warranted due to the vast number of scanning and analysis parameters. However, our analysis suggests that researchers can optimize their individual processing procedures with respect to final segmentation quality and exemplifies adequate performance criteria.
The neurobiological basis of non-organic movement impairments is still unknown. As conversion disorder and hypnotic states share many characteristics, we applied an experimental design established in conversion disorder to investigate hypnotic paralysis.
The conceptual notion of the so-called resting state of the brain has been recently challenged by studies indicating a continuing effect of cognitive processes on subsequent rest. In particular, activity in posterior parietal and medial prefrontal areas has been found to be modulated by preceding experimental conditions. In this study, we investigated which brain areas show working memory dependent patterns in subsequent baseline periods and how specific they are for the preceding experimental condition. During functional magnetic resonance imaging, 94 subjects performed a letter-version of the n-back task with the conditions 0-back and 2-back followed by a low-level baseline in which subjects had to passively observe the letters appearing. In a univariate analysis, 2-back served as control condition while 0-back, baseline after 0-back and baseline after 2-back were modeled as regressors to test for activity changes between both baseline conditions. Additionally, we tested, using Gaussian process classifiers, the recognition of task condition from functional images acquired during baseline. Besides the expected activity changes in the precuneus and medial prefrontal cortex, we found differential activity in the thalamus, putamen, and postcentral gyrus that were affected by the preceding task. The multivariate analysis revealed that images of the subsequent baseline block contain task related patterns that yield a recognition rate of 70%. The results suggest that the influence of a cognitive task on subsequent baseline is strong and specific for some areas but not restricted to areas of the so-called default mode network.
Causality provides a natural structure for organizing our experience and language. Causal reasoning during speech production is a distinct aspect of verbal communication, whose related brain processes are yet unknown. The aim of the current study was to investigate the neural mechanisms underlying the continuous generation of cause-and-effect coherences during overt word production. During fMRI data acquisition participants performed three verbal fluency tasks on identical cue words: A novel causal verbal fluency task (CVF), requiring the production of multiple reasons to a given cue word (e.g. reasons for heat are fire, sun etc.), a semantic (free association, FA, e.g. associations with heat are sweat, shower etc.) and a phonological control task (phonological verbal fluency, PVF, e.g. rhymes with heat are meat, wheat etc.). We found that, in contrast to PVF, both CVF and FA activated a left lateralized network encompassing inferior frontal, inferior parietal and angular regions, with further bilateral activation in middle and inferior as well as superior temporal gyri and the cerebellum. For CVF contrasted against FA, we found greater bold responses only in the left middle frontal cortex. Large overlaps in the neural activations during free association and causal verbal fluency indicate that the access to causal relationships between verbal concepts is at least partly based on the semantic neural network. The selective activation in the left middle frontal cortex for causal verbal fluency suggests that distinct neural processes related to cause-and-effect-relations are associated with the recruitment of middle frontal brain areas.
Crossed language dominance is a rare form of language lateralization, characterized by a dissociation of anterior and posterior language regions. We present the case of a healthy subject whose language lateralization pattern, as assessed by functional magnetic resonance imaging, is reliably characterized as crossed language dominance based on a word generation task, but typical left-lateralized when a semantic decision task is applied. A single language task is therefore not sufficient to characterize language lateralization, at least not for subjects with rare forms of language dominance. In the pre-surgical diagnostic of language lateralization, several language tasks tapping into different aspects of language functions should be applied.
The common single-nucleotide polymorphism (SNP) brain-derived neurotrophic factor (BDNF) valine-to-methionine substitution at codon 66 (Val66Met) has been associated with differences in memory functions and cortical plasticity following brain stimulation. Other studies could not confirm these results, though, and potential interactions of BDNF carrier status with other learning-relevant SNPs are largely unknown. The present study aimed to evaluate the effects of BDNF Val66Met genotype on paired associative stimulation (PAS)-induced motor cortex plasticity, while additionally taking catechol-O-methyltransferase (COMT) Val158Met and kidney and brain (KIBRA) rs17070145 carrier status into account. Therefore, a cohort of 2 × 16 age- and education-matched healthy young females underwent transcranial magnetic stimulation using an excitatory PAS(25) protocol to induce cortical plasticity. Cognitive performance was assessed using implicit grammar- and motor-learning tasks and a detailed neuropsychological test battery. While BDNF carrier status alone did not significantly influence PAS-induced cortical plasticity, we found a significant BDNF × COMT interaction, showing higher plasticity immediately following the PAS(25) protocol for the BDNF Val/Val vs Met genotype in COMT Met homozygotes only (ANOVA, p = 0.027). A similar advantage for this group was noted for implicit grammar learning (ANOVA, p = 0.021). Accounting for KIBRA rs17070145 did not explain significant variance. Our findings for the first time demonstrate an interaction of BDNF by COMT on human cortical plasticity. Moreover, they show that genotype-related differences in neurophysiology translate into behavioral differences. These findings might contribute to a better understanding of the mechanisms of interindividual differences in cognition.
Identifying structure formation in semicrystalline conjugated polymers is the fundamental basis to understand electronic processes in these materials. Although correlations between physical properties, structure formation, and device parameters of regioregular, semicrystalline poly(3-hexylthiophene) (P3HT) have been established, it has remained difficult to disentangle the influence of regioregularity, polydispersity, and molecular weight. Here we show that the most commonly used synthetic protocol for the synthesis of P3HT, the living Kumada catalyst transfer polycondensation (KCTP) with Ni(dppp)Cl(2) as the catalyst, leads to regioregular chains with one single tail-to-tail (TT) defect distributed over the whole chain, in contrast to the hitherto assumed exclusive location at the chain end. NMR end-group analysis and simulations are used to quantify this effect. A series of entirely defect-free P3HT materials with different molecular weights is synthesized via new, soluble nickel initiators. Data on structure formation in defect-free P3HT, as elucidated by various calorimetric and scattering experiments, allow the development of a simple model for estimating the degree of crystallinity. We find very good agreement for predicted and experimentally determined degrees of crystallinities as high as ?70%. For Ni(dppp)Cl(2)-initiated chains comprising one distributed TT unit, the comparison of simulated crystallinities with calorimetric and optical measurements strongly suggests incorporation of the TT unit into the crystal lattice, which is accompanied by an increase in backbone torsion. Polydispersity is identified as a major parameter determining crystallinity within the molecular weight range investigated. We believe that the presented approach and results not only contribute to understanding structure formation in P3HT but are generally applicable to other semicrystalline conjugated polymers as well.
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