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An effective dynamical description of a general class of stochastic phase oscillators is presented. For this, the effective phase velocity is defined either by the stochastic phase oscillators invariant probability density or its first passage times. Using the first approach the effective phase exhibits the correct frequency and invariant distribution density, whereas the second approach models the proper phase resetting curve. The discrepancy of the effective models is most pronounced for noise-induced oscillations and is related to non-monotonicity of the stochastic phase variable due to fluctuations.
We develop an effective description of noise-induced oscillations based on deterministic phase dynamics. The phase equation is constructed to exhibit correct frequency and distribution density of noise-induced oscillations. In the simplest one-dimensional case the effective phase equation is obtained analytically, whereas for more complex situations a simple method of data processing is suggested. As an application an effective coupling function is constructed that quantitatively describes periodically forced noise-induced oscillations.
We consider large populations of phase oscillators with global nonlinear coupling. For identical oscillators such populations are known to demonstrate a transition from completely synchronized state to the state of self-organized quasiperiodicity. In this state phases of all units differ, yet the population is not completely incoherent but produces a nonzero mean field; the frequency of the latter differs from the frequency of individual units. Here we analyze the dynamics of such populations in case of uniformly distributed natural frequencies. We demonstrate numerically and describe theoretically (i) states of complete synchrony, (ii) regimes with coexistence of a synchronous cluster and a drifting subpopulation, and (iii) self-organized quasiperiodic states with nonzero mean field and all oscillators drifting with respect to it. We analyze transitions between different states with the increase of the coupling strength; in particular we show that the mean field arises via a discontinuous transition. For a further illustration we compare the results for the nonlinear model with those for the Kuramoto-Sakaguchi model.
We report on a self-emerging chimera state in a homogeneous chain of nonlocally and nonlinearly coupled oscillators. This chimera, i.e., a state with coexisting regions of complete and partial synchrony, emerges via a supercritical bifurcation from a homogeneous state. We develop a theory of chimera based on the Ott-Antonsen equations for the local complex order parameter. Applying a numerical linear stability analysis, we also describe the instability of the chimera and transition to phase turbulence with persistent patches of synchrony.
Inelastic x-ray scattering spectra excited at the 1s(-1) pi* resonance of gas phase O-2 have been recorded with an overall energy resolution that allows for well-resolved vibrational progressions. The nuclear wave packet dynamics in the intermediate state is reflected in vibrational excitations of the electronic ground state, and by fine-tuning the excitation energy the dissociation dynamics in the predissociative B' (3) Pi(g) final state is controlled.
The application of the architectural concept of service-oriented architectures (SOA) in combination with open standards when building distributed, 3D geovisualization systems offers the potential to cover and take advantage of the opportunities and demands created by the rise of ubiquitous computer networks and the Internet as well as to overcome prevalent interoperability barriers. In this paper, based on a literature study and our own experiences, we discuss the potential and challenges that arise when building standards-based, distributed systems according to the SOA paradigm for 3D geovisualization, with a particular focus on 3D geovirtual environments and virtual 3D city models. First, we briefly introduce fundamentals of the SOA paradigm, identify requirements for service-oriented 3D geovisualization systems, and present an architectural framework that relates SOA concepts, geovisualization concepts, and standardization proposals by the Open Geospatial Consortium in a common frame of reference. Next, we discuss the potential and challenges driven by the SOA paradigm on four different levels of abstraction, namely service fundamentals, service composition, interaction services, performance, and overarching aspects, and we discuss those driven by standardization. We further exemplify and substantiate the discussion in the scope of a case study and the image-based provisioning of and interaction with visual representations of remote virtual 3D city models.
Earthquake rupture length and width estimates are in demand in many seismological applications. Earthquake magnitude estimates are often available, whereas the geometrical extensions of the rupture fault mostly are lacking. Therefore, scaling relations are needed to derive length and width from magnitude. Most frequently used are the relationships of Wells and Coppersmith (1994) derived on the basis of a large dataset including all slip types with the exception of thrust faulting events in subduction environments. However, there are many applications dealing with earthquakes in subduction zones because of their high seismic and tsunamigenic potential. There are no well-established scaling relations for moment magnitude and length/width for subduction events. Within this study, we compiled a large database of source parameter estimates of 283 earthquakes. All focal mechanisms are represented, but special focus is set on (large) subduction zone events, in particular. Scaling relations were fitted with linear least-square as well as orthogonal regression and analyzed regarding the difference between continental and subduction zone/oceanic relationships. Additionally, the effect of technical progress in earthquake parameter estimation on scaling relations was tested as well as the influence of different fault mechanisms. For a given moment magnitude we found shorter but wider rupture areas of thrust events compared to Wells and Coppersmith (1994). The thrust event relationships for pure continental and pure subduction zone rupture areas were found to be almost identical. The scaling relations differ significantly for slip types. The exclusion of events prior to 1964 when the worldwide standard seismic network was established resulted in a remarkable effect on strike-slip scaling relations: the data do not show any saturation of rupture width of strike- slip earthquakes. Generally, rupture area seems to scale with mean slip independent of magnitude. The aspect ratio L/W, however, depends on moment and differs for each slip type.
Recent calculations on the hydrogen-exchange reaction [Bouakline et al., J. Chem. Phys. 128, 124322 (2008)], have found strong geometric phase (GP) effects in the state-to-state differential cross-sections (DCS), at energies above the energetic minimum of the conical intersection (CI) seam, which cancel out in the integral cross-sections (ICS). In this article, we explain the origin of this cancellation and make other predictions about the nature of the reaction mechanisms at these high energies by carrying out quasiclassical trajectory (QCT) calculations. Detailed comparisons are made with the quantum results by splitting the quantum and the QCT cross-sections into contributions from reaction paths that wind in different senses around the CI and that scatter the products in the nearside and farside directions. Reaction paths that traverse one transition state (1-TS) scatter their products in just the nearside direction, whereas paths that traverse two transition states (2-TS) scatter in both the nearside and farside directions. However, the nearside 2-TS products scatter into a different region of angular phase-space than the 1-TS products, which explains why the GP effects cancel out in the ICS. Analysis of the QCT results also suggests that two separate reaction mechanisms may be responsible for the 2-TS scattering at high energies.
A considerable fraction of the central stars of planetary nebulae (CSPNe) are hydrogen-deficient. As a rule, these CSPNe exhibit a chemical composition of helium, carbon, and oxygen with the majority showing Wolf-Rayet-like emission line spectra. These stars are classified as CSPNe of a spectral type [WC]. We perform a spectral analysis of CSPN PB 8 with the Potsdam Wolf-Rayet (PoWR) models for expanding atmospheres. The source PB8 displays wind-broadened emission lines from strong mass loss. Most strikingly, we find that its surface composition is hydrogen-deficient, but not carbon-rich. With mass fractions of 55% helium, 40% hydrogen, 1.3% carbon, 2% nitrogen, and 1.3% oxygen, it differs greatly from the 30-50% of carbon which are typically seen in [WC]-type central stars. The atmospheric mixture in PB8 has an analogy in the WN/WC transition type among the massive Wolf-Rayet stars. Therefore we suggest to introduce a new spectral type [WN/WC] for CSPNe, with PB8 as its first member. The central star of PB8 has a relatively low temperature of T-* = 52 kK, as expected for central stars in their early evolutionary stages. Its surrounding nebula is less than 3000 years old, i.e. relatively young. Existing calculations for the post-AGB evolution can produce hydrogen-deficient stars of the [WC] type, but do not predict the composition found in PB8. We discuss various scenarios that might explain the origin of this unique object.
Seasonal precipitation gradients and their impact on fluvial sediment flux in the Northwest Himalaya
(2010)
Precipitation in the form of rain and snowfall throughout the Himalaya controls river discharge and erosional processes and, thus, has a first-order control on the fluvial sediment flux. Here, we analyze daily precipitation data (1998-2007) of 80 weather stations from the northwestern Himalaya in order to decipher temporal and spatial moisture gradients. In addition, suspended sediment data allow assessment of the impact of precipitation on the fluvial sediment flux for a 10(3)-km(2) catchment (Baspa). We find that weather stations located at the mountain front receive similar to 80% of annual precipitation during summer (May-Oct), whereas stations in the orogenic interior, i.e., leeward of the orographic barrier, receive similar to 60% of annual precipitation during winter (Nov-Apr). In both regions 4-6 rainstorm days account for similar to 40% of the summer budgets, while rainstorm magnitude-frequency relations, derived from 40-year precipitation time-series, indicate a higher storm variability in the interior than in the frontal region. This high variability in maximum annual rainstorm days in the orogenic interior is reflected by a high variability in extreme suspended sediment events in the Baspa Valley, which strongly affect annual erosion yields. The two most prominent 5-day-long erosional events account for 50% of the total 5-year suspended sediment flux and coincide with synoptic-scale monsoonal rainstorms. This emphasizes the erosional impact of the Indian Summer Monsoon as the main driving force for erosion processes in the orogenic interior, despite more precipitation falling during the winter season.
In research on eye-movement control during reading, the importance of cognitive processes related to language comprehension relative to visuomotor aspects of saccade generation is the topic of an ongoing debate. Here we investigate various eye-movement measures during reading of randomly shuffled meaningless text as compared to normal meaningful text. To ensure processing of the material, readers were occasionally probed for words occurring in normal or shuffled text. For reading of shuffled text we observed longer fixation times, less word skippings, and more refixations than in normal reading. Shuffled-text reading further differed from normal reading in that low-frequency words were not overall fixated longer than high-frequency words. However, the frequency effect was present on long words, but was reversed for short words. Also, consistent with our prior research we found distinct experimental effects of spatially distributed processing over several words at a time, indicating how lexical word processing affected eye movements. Based on analyses of statistical linear mixed-effect models we argue that the results are compatible with the hypothesis that the perceptual span is more strongly modulated by foveal load in the shuffled reading task than in normal reading. Results are discussed in the context of computational models of reading.
Eye movements during the reading of multi-line pages of texts were analyzed to determine the trajectory of reading saccades. The results of two experiments showed that the trajectory of the majority of forward-directed saccades was negatively biased, i.e., the trajectory fell below the start and end location of the saccadic movement. This is attributed to a global top-to-bottom orienting of attention. The curvature size and the proportion of negative trajectories were diminished when linguistic processing demands were high and when the beginning lines of a page were read. Longer pre-saccadic fixations also yielded smaller saccadic curvatures, and they resulted in fewer negatively curved forward-directed saccades in Experiment 1 although not in Experiment 2. These findings indicate that the top-to- bottom pull of saccadic trajectories is modulated by processing demands and processing opportunities. The results are in general agreement with a time-locked attraction-inhibition hypothesis, according to which the horizontal movement component of a saccade is initially subject to an automatic top-to-bottom orienting of attention that is subsequently inhibited.
e movements during the reading of multi-line pages of texts were analyzed to determine the trajectory of reading saccades. The results of two experiments showed that the trajectory of the majority of forward-directed saccades was negatively biased, i.e., the trajectory fell below the start and end location of the saccadic movement. This is attributed to a global top-to-bottom orienting of attention. The curvature size and the proportion of negative trajectories were diminished when linguistic processing demands were high and when the beginning lines of a page were read. Longer pre-saccadic fixations also yielded smaller saccadic curvatures, and they resulted in fewer negatively curved forward-directed saccades in Experiment 1 although not in Experiment 2. These findings indicate that the top-to- bottom pull of saccadic trajectories is modulated by processing demands and processing opportunities. The results are in general agreement with a time-locked attraction-inhibition hypothesis, according to which the horizontal movement component of a saccade is initially subject to an automatic top-to-bottom orienting of attention that is subsequently inhibited.
Kapitalaufbringung und verdreckte Sacheinlagen bei der Aktienplatzierung durch Emissionsbanken
(2010)
Gelatin is a non-immunogenic and degradable biopolymer, which is widely applied in the biomedical field e. g. for drug capsules or as absorbable hemostats. However, gelatin materials present limited and hardly reproducible mechanical properties especially in aqueous systems, particularly caused by the uncontrollable partial renaturation of collagen-like triple helices. Therefore, mechanically demanding applications for gelatin-based materials, such as vascular patches, i.e. hydrogel films that seal large incisions in vessel walls, and for induced autoregeneration, are basically excluded if this challenge is not addressed. Through the synthesis of a defined chemical network of gelatin with hexamethylene diisocyanate (HDI) in DMSO, the self-organization of gelatin chains could be hindered and amorphous gelatin films were successfully prepared having Young's moduli of 60-530 kPa. Transferring the crosslinking reaction with HDI and, alternatively, ethyl lysine diisocyanate (LDI), to water as reaction medium allowed the tailoring of swelling behaviour and mechanical properties by variation of crosslinker content while suppressing the formation of helices. The hydrogels had Young's moduli of 70-740 kPa, compressive moduli of 16-48 kPa, and degrees of swelling of 300-800 vol%. Test reactions investigated by ESI mass spectrometry allowed the identification and quantification of reaction products of the crosslinking reaction. The HDI crosslinked networks were stabilized by direct covalent crosslinks (ca. 10 mol%), supported by grafting (50 mol%) and blending of hydrophobic oligomeric chains. For the LDI- based networks, less crosslinked (3 mol%) and grafted species (5 mol%) and much higher amounts of oligomers were observed. The adjustable hydrogel system enables the application of gelatin-based materials in physiological environments.
Growth and body height have always been topics interesting to the public. In particular, the stupendous increase of some 15-19 cm in final adult height during the last 150 years in most European countries (the "secular trend"), the concomitant changes in body and head proportions, the tendency towards early onset of sexual maturation, the changes in the age when final height is being reached, and the very recent trend in body mass index, have generated much scientific literature. The marked plasticity of growth in height and weight over time causes problems. Child growth references differ between nations, they tend to quickly become out of date, and raise a number of questions regarding fitting methods, effects caused by selective drop-out, etc. New findings contradict common beliefs about the primary importance of nutritional and health related factors for secular changes in growth. There appears to be a broad age span from mid-childhood to early adolescence that is characterised by a peculiar insusceptibility. Environmental factors that are known to influence growth during this age span appear to have only little or no impact on final height. Major re- arrangements in height occur at an age when puberty has almost been completed and final height has almost been reached, implying that factors, which drive the secular trend in height, are limited to early childhood and late adolescence.
The aim of this methodological anthropometric study was to compare direct anthropometry and digital two- dimensional photogrammetry in 18 male and 27 female subjects, aged 24 to 65 years, from Potsdam, Germany. In view of the rising interest in reliable biometric kephalofacial data, we focussed on head and face measurements. Out of 34 classic facial anatomical landmarks, 27 landmarks were investigated both by direct anthropometry and 2D-photogrammetry; 7 landmarks could not be localized by 2D-photogrammetry. Twenty-six kephalofacial distances were analysed both by direct anthropometry and digital 2D-photogrammetry. Kephalofacial distances are on average 7.6% shorter when obtained by direct anthropometry. The difference between the two techniques is particularly evident in total head height (vertex-gnathion) due to the fact that vertex is usually covered by hair and escapes from photogrammetry. Also the distances photographic sellion-gnathion (1.3 cm, i. e. 11.6%) and nasal-gnathion (1.2 cm, i. e. 9.4%) differ by more than one centimetre. Differences below 0.5 cm between the two techniques were found when measuring mucosa-lip-height (2.2%), gonia (3.0%), glabella-stomion (3.9%), and nose height (glabella-subnasal) (4.0%). Only the estimates of forehead width were significantly narrower when obtained by 2D-photogrammetry (-1.4 cm, -13.1%). The methodological differences increased with increasing magnitude of the kephalometric distance. Apart from these limitations, both techniques are similarly valid and may replace each other.
Ample literature describes the history of the association between the advances in the health and wealth of people, and mortality rates, life expectancy and adult height. Twentynine German studies with n > 200 subjects published since 1848 on menarcheal age, were reanalyzed, and 101 studies from various other European and non-European countries. On average, mean age at menarche declined since the mid-19(th) century. Historic urban samples tended to decline earlier than rural groups, upper class women earlier than working class women. In Germany, minimum values for the age at menarche were seen already between the two World Wars (Leipzig 12.6 years in 1934, Halle 13.3 years in 1939). Values for mean age and SD for age at menarche were strongly associated. With improving historic circumstances, the two parameters declined in parallel. The standard deviation for menarcheal age dropped from over 2.5 years in mid-19th century France to little more or even less than 1 year in most modern countries. In the German studies the correlation between menarcheal age and SD was almost complete with r = 0.96 (y = 0.35x - 3.53). Similar associations between mean age at menarche and SD for age were found in other European countries. The obvious and immediate effects of historic events on menarcheal age, and particularly on the age distribution, indicate that menarche is a sensitive indicator of public health and wealth, and may be an appropriate estimator for the socio-economic background of historic populations.
Recent progress in modelling individual growth has been achieved by combining the principal component analysis and the maximum likelihood principle. This combination models growth even in incomplete sets of data and in data obtained at irregular intervals. We re-analysed late 18th century longitudinal growth of German boys from the boarding school Carlsschule in Stuttgart. The boys aged 6-23 years, were measured at irregular 3-12 monthly intervals during the period 1771-1793. At the age of 18 years, mean height was 1652 mm, but height variation was large. The shortest boy reached 1474 mm, the tallest 1826 mm. Measured height closely paralleled modelled height, with mean difference of 4 mm, SD 7 mm. Seasonal height variation was found. Low growth rates occurred in spring and high growth rates in summer and autumn. The present study demonstrates that combining the principal component analysis and the maximum likelihood principle enables growth modelling in historic height data also.
Fehrbellin
(2010)
The report shows that simple LbL deposition of positively charged chitosan and negatively charged heparin can be used to efficiently modify the native surface of both NiTi and Ti without any previous treatments. Moreover, mineralization of the polymer multilayers with calcium phosphate leads to surfaces with low contact angles around 70 and 20 degrees for NiTi and Ti, respectively. This suggests that a polymer multilayer/calcium phosphate hybrid coating could be useful for making NiTi or Ti implants that are at the same time antibacterial (via the chitosan), suppress blood clot formation (via the heparin), and favor fast endothelialization (via the improved surface hydrophilicity compared to the respective neat material).
We report on attempts towards the synthesis of titanium nanoparticles using a wet chemical approach in imidazolium-based ionic liquids (ILs) under reducing conditions. Transmission electron microscopy finds nanoparticles in all cases. UV/Vis spectroscopy confirms the nanoparticulate nature of the precipitate, as in all cases an absorption band between ca. 280 and 300 nm is visible. IR spectroscopy shows that even after extensive washing and drying, some IL remains adsorbed on the nanoparticles. Raman spectroscopy suggests the formation of anatase nanoparticles, but X-ray diffraction reveals that, possibly, amorphous titania forms or that the nanoparticles are so small that a clear structure assignment is not possible. The report thus shows that (possibly amorphous) titanium oxides even form under reducing conditions and that the chemical synthesis of titanium nanoparticles in ILs remains elusive.
There is growing evidence that aging and muscle fatigue result in impaired postural reflexes in humans. Therefore, the objective of this study was to examine the effects of ankle fatigue on functional reflex activity (ERA) during gait perturbations in young and elderly men. Twenty-eight young (27.0 +/- 3.1 years, n = 14) and old (67.2 +/- 3.7 years, n = 14) healthy active men participated in this study. Fatigue of the plantarflexors and dorsiflexors was induced by isokinetic contractions. Pre and post-fatigue, subjects were tested for their ability to compensate for decelerating gait perturbations while walking on a treadmill. Latency, ERA of lower extremity muscles and angular velocity of the ankle joint complex were analysed by means of surface electromyography and goniometry. After the fatigue protocol, no significant main and interaction effects were detected for the parameter latency in m. tibialis anterior (TA). For both groups, a significant pre to post-test decrease in ERA in TA (P<.001) was observed coming along with increases in antagonist coactivity (P=.013) and maximal angular velocity of the ankle joint (p=.007). However, no significant group x test interactions were found for the three parameters. Ankle fatigue has an impact on the ability to compensate for gait perturbations in young and elderly adults. However, no significant differences in all analysed parameters were detected between young and elderly subjects. These results may imply that age-related deteriorations in the postural control system do not specifically affect the ability to compensate for gait perturbations under fatigued condition.
The red clover isoflavone irilone is largely resistant to degradation by the human gut microbiota
(2010)
Intestinal bacteria may influence bioavailability and physiological activity of dietary isoflavones. We therefore investigated the ability of human intestinal microbiota to convert irilone and genistein in vitro. In contrast to genistein, irilone was largely resistant to transformation by fecal slurries of ten human subjects. The fecal microbiota converted genistein to dihydrogenistein, 6'-hydroxy-O-desmethylangolensin, and 2-(4-hydroxyphenyl)- propionic acid. However, considerable interindividual differences in the rate of genistein degradation and the pattern of metabolites formed from genistein were observed. Only one metabolite, namely dihydroirilone, was formed from irilone in minor amounts. In further experiments, Eubacterium ramulus, a prevalent flavonoid-degrading species of the human gut, was tested for transformation of irilone. In contrast to genistein, irilone was not converted by E. ramulus. Irilone only differs from genistein by a methylenedioxy group attached to the A-ring of the isoflavone skeleton. This substitution obviously restricts the degradability of irilone by human intestinal bacteria.
Le possiblili vite di un artista : Andrea De Carlo e la varietá delle sue alteritá immaginate
(2010)
Physikalisches Wissen und ästhetische Darstellung in Sur les nuages (1888) von Guy de Maupassant
(2010)
Einleitung
(2010)
We investigate the large-scale oceanic features determining the future ice shelf-ocean interaction by analyzing global warming experiments in a coarse resolution climate model with a comprehensive ocean component. Heat and freshwater fluxes from basal ice shelf melting (ISM) are parameterized following Beckmann and Goosse [Ocean Model 5(2):157-170, 2003]. Melting sensitivities to the oceanic temperature outside of the ice shelf cavities are varied from linear to quadratic (Holland et al. in J Clim 21, 2008). In 1% per year CO2-increase experiments the total freshwater flux from ISM triples to 0.09 Sv in the linear case and more than quadruples to 0.15 Sv in the quadratic case after 140 years at which 4 x 280 ppm = 1,120 ppm was reached. Due to the long response time of subsurface temperature anomalies, ISM thereafter increases drastically, if CO2 concentrations are kept constant at 1,120 ppm. Varying strength of the Antarctic circumpolar current (ACC) is crucial for ISM increase, because southward advection of heat dominates the warming along the Antarctic coast. On centennial timescales the ACC accelerates due to deep ocean warming north of the current, caused by mixing of heat along isopycnals in the Southern Ocean (SO) outcropping regions. In contrast to previous studies we find an initial weakening of the ACC during the first 150 years of warming. This purely baroclinic effect is due to a freshening in the SO which is consistent with present observations. Comparison with simulations with diagnosed ISM but without its influence on the ocean circulation reveal a number of ISM-related feedbacks, of which a negative ISM-feedback, due to the ISM-related local oceanic cooling, is the dominant one.
The 8.2 ka event : abrupt transition of the subpolar gyre toward a modern North Atlantic circulation
(2010)
Climate model simulations of the 8.2 ka event show an abrupt strengthening of the Atlantic subpolar gyre that allows us to connect two major but apparently contradictory climate events of the early Holocene: the freshwater outburst from proglacial lakes and the onset of Labrador Sea water formation. The 8.2 ka event is the largest climatic signal of our present interglacial with a widespread cooling in the North Atlantic region about 8200 years before present. It coincides with a meltwater outburst from North American proglacial lakes that is believed to have weakened the Atlantic meridional overturning circulation and northward heat transport, followed by a recovery of the deep ocean circulation and rising temperatures after a few centuries. Marine proxy data, however, date the onset of deep water formation in Labrador Sea to the same time. The subsequent strengthening of the slope current system created a regional signal recorded as an abrupt and persistent surface temperature decrease. Although similarities in timing are compelling, a mechanism to reconcile these apparently contradictory events was missing. Our simulations show that an abrupt and persistent strengthening of the Atlantic subpolar gyre provides a plausible explanation. The intense freshwater pulse triggered a transition of the gyre circulation into a different mode of operation, stabilized by internal feedbacks and persistent after the cessation of the perturbation. As a direct consequence, deep water formation around its center intensifies. This corresponds to the modern flow regime and stabilizes the meridional overturning circulation, possibly contributing to the Holocene's climatic stability.
We have studied I lie thermal behavior of amphiphilic, symmetric triblock copolymers having short, deuterated polystyrene (PS) end blocks and a large poly(N-isopropylacrylarnicle) (PNIPAM) middle block exhibiting a lower critical solution temperature (LCST) in aqueous solution. A wide range of concentrations (0.1-300 mg/mL) is investigated using it number of analytical methods such as fluorescence correlation spectroscopy (FCS), turbidimetry, dynamic light scattering (DLS), small-angle neutron scattering (SANS), and neutron spin-echo spectroscopy (NSE). The critical micelle concentration is determined using FCS to be 1 mu M or less. The collapse of the micelles at the LCST is investigated using turbidimetry and DLS and shows a weak dependence on the degree of polymerization of the PNIPAM block. SANS with contrast matching allows its to reveal the core-shell Structure of the micelles as well as their correlation as a function of temperature. The segmental dynamics of the PNIPAM shell are studied as a function of temperature and arc found to be faster in the collapsed state than in the swollen state. The mode detected has a linear dispersion in q(2) and is found to be faster in the collapsed state as compared to the swollen state. We attribute this result to the averaging over mobile and immobilized segments.
Several series of symmetrical triblock copolymers were synthesized by the reversible addition fragmentation chain transfer method. They consist of a long block of poly(N-isopropylacrylamide) as hydrophilic, thermoresponsive middle block, which is end-capped by two small strongly hydrophobic blocks made from five different vinyl polymers. The association of the amphiphilic polymers was studied in dilute and concentrated aqueous solution. The polymer micelles found at low concentrations form hydrogels at high concentrations, typically above 30-35 wt.%. Hydrogel formation and the thermosensitive rheological behavior were studied exemplarily for copolymers with hydrophobic blocks of polystyrene, poly(2-ethylhexyl acrylate), and poly(n-octadecyl acrylate). All systems exhibited a cloud point around 30 A degrees C. Heating beyond the cloud point initially favors hydrogel formation but continued heating results in macroscopic phase separation. The rheological behavior suggests that the copolymers associate into flower-like micelles, with only a small share of polymers that bridge the micelles and act as physical cross-linkers, even at high concentrations.