1,721,003 research outputs found
Azobenzene isomerization in condensed matter: lessons for the design of efficient light-responsive soft-matter systems
Get PDFAzobenzene-based materials have found applications in a wide variety of systems as a convenient method to induce photo-responsive behaviour through facile trans (E) to cis (Z) isomerization. Of particular interest are condensed matter systems, for which diverse assemblies have been applied in myriad ways to produce optical materials, controllable assemblies and functional surfaces. However, isomerization of azobenzene faces unique challenges in condensed systems when compared with dilute states (molecular solution and gas phase) where isomerization is best understood. In the present work, we explore recent studies looking at these challenges experienced in condensed matter phases, some solutions proposed to improve isomerization efficiency, and further give these issues wider context for the future development of light-responsive soft-matter systems
Interface-induced hysteretic volume phase transition of microgels: simulation and experiment
Get PDFThermo-responsive microgel particles can exhibit a drastic volume shrinkage
upon increasing the solvent temperature. Recently we found that the spreading
of poly(N-isopropylacrylamide)(PNiPAm) microgels at a liquid interface under
the influence of surface tension hinders the temperature-induced volume phase
transition. In addition, we observed a hysteresis behavior upon temperature
cycling, i.e. a different evolution in microgel size and shape depending on
whether the microgel was initially adsorbed to the interface in expanded or
collapsed state. Here, we model the volume phase transition of such microgels
at an air/water interface by monomer-resolved Brownian dynamics simulations and
compare the observed behavior with experiments. We reproduce the experimentally
observed hysteresis in the microgel dimensions upon temperature variation. Our
simulations did not observe any hysteresis for microgels dispersed in the bulk
liquid, suggesting that it results from the distinct interfacial morphology of
the microgel adsorbed at the liquid interface. An initially collapsed microgel
brought to the interface and subjected to subsequent swelling and collapsing
(resp. cooling and heating) will end up in a larger size than it had in the
original collapsed state. Further temperature cycling, however, only shows a
much reduced hysteresis, in agreement with our experimental observations. We
attribute the hysteretic behavior to a kinetically trapped initial collapsed
configuration, which relaxes upon expanding in the swollen state. We find a
similar behavior for linear PNiPAm chains adsorbed to an interface. Our
combined experimental - simulation investigation provides new insights into the
volume phase transition of PNiPAm materials adsorbed to liquid interfaces
Self-stresses control stiffness and stability in overconstrained disordered networks
Get PDFWe investigate the interplay between prestress and mechanical properties in random elastic networks. To do this in a controlled fashion, we introduce an algorithm for creating random free-standing frames that support exactly one state of self-stress. By multiplying all the bond tensions in this state of self-stress by the same number-which with the appropriate normalization corresponds to the physical prestress inside the frame-we systematically evaluate the linear mechanical response of the frame as a function of prestress. After proving that the mechanical moduli of affinely deforming frames are rigorously independent of prestress, we turn to nonaffinely deforming frames. In such frames, prestress has a profound effect on linear response: not only can it change the values of the linear modulus-an effect we demonstrate to be related to a suppressive effect of prestress on nonaffinity-but prestresses also generically trigger a bistable mechanical response. Thus, prestress can be leveraged to both augment the mechanical response of network architectures on the fly, and to actuate finite deformations. These control modalities may be of use in the design of both novel responsive materials and soft actuators
Collapse-induced phase transitions in binary interfacial microgel monolayers
Get PDFMicrogels, consisting of a swollen polymer network, exhibit a more complex self-assembly behavior compared to incompressible colloidal particles, because of their ability to deform at a liquid interface or collapse upon compression. Here, we investigate the collective phase behavior of two-dimensional binary mixtures of microgels confined at the air/water interface. We use stimuli-responsive poly(N-isopropylacrylamide) microgels with different crosslinking densities, and therefore different morphologies at the interface. We find that the minority microgel population introduces lattice defects in the ordered phase of the majority population, which, in contrast to bulk studies, do not heal out by partial deswelling to accommodate in the lattice. We subsequently investigate the interfacial phase behavior of these binary interfacial assemblies under compression. The binary system exhibits three distinct isostructural solid-solid phase transitions, during which the coronae between two small particles collapse first, followed by the collapse between small-large and large-large microgel pairs. A similar hierarchy of phase transitions is found for mixtures of microgels and core-shell particles. Simulations based on augmented potentials qualitatively reproduce the experimentally observed phase transitions. We rationalize the presence of this hierarchy in phase transitions from differences in the interfacial morphology between the species: the larger coronae of softer (and therefore larger) microgels provide a higher resistance to phase transitions compared to the smaller coronae of the more crosslinked microgels and core-shell particles. The control of phase transitions via the molecular architecture further allows the formation of characteristic, flower-like defects by introducing particles with "weaker"coronae that are more prone to collapse with their neighboring particles. Our findings underline the dominating role of the corona for interfacial microgel assemblies, which acts as an energy barrier, shifting the collapse to higher surface pressures
Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Get PDF“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Get PDFWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
Stimuli-responsive behavior of PNiPAm microgels under interfacial confinement
Get PDFThe volume phase transition of microgels is one of the most paradigmatic examples of stimuli-responsiveness, enabling a collapse from a highly swollen microgel state into a densely coiled state by an external stimulus. Although well characterized in bulk, it remains unclear how the phase transition is affected by the presence of a confining interface. Here, we demonstrate that the temperature-induced volume phase transition of poly(N-isopropylacrylamide) microgels, conventionally considered an intrinsic molecular property of the polymer, is in fact largely suppressed when the microgel is adsorbed to an air/liquid interface. We further observe a hysteresis in the core morphology and interfacial pressure between heating and cooling cycles. Our results, supported by molecular dynamics simulations, reveal that the dangling polymer chains of microgel particles, spread at the interface under the influence of surface tension, do not undergo any volume phase transition. The balance in free energy responsible for the volume phase transition is fundamentally altered by interfacial confinement. These results imply that important technological properties of such systems, including the temperature-induced destabilization of emulsions, do not occur via a decrease in the interfacial coverage of the microgels
Multi-component generalized mode-coupling theory: predicting dynamics from structure in glassy mixtures
Get PDFAbstract: The emergence of glassy dynamics and the glass transition in dense disordered systems is still not fully understood theoretically. Mode-coupling theory (MCT) has shown to be effective in describing some of the non-trivial features of glass formation, but it cannot explain the full glassy phenomenology due to the strong approximations on which it is based. Generalized mode-coupling theory (GMCT) is a hierarchical extension of the theory, which is able to outclass MCT by carefully describing the dynamics of higher-order correlations in its generalized framework. Unfortunately, the theory has so far only been developed for single-component systems and as a result works poorly for highly polydisperse materials. In this paper, we solve this problem by developing GMCT for multi-component systems. We use it to predict the glassy dynamics of the binary Kob–Andersen Lennard-Jones mixture, as well as its purely repulsive Weeks–Chandler–Andersen analogue. Our results show that each additional level of the GMCT hierarchy gradually improves the predictive power of GMCT beyond its previous limit. This implies that our theory is able to harvest more information from the static correlations, thus being able to better understand the role of attraction in supercooled liquids from a first-principles perspective. Graphic abstract: [Figure not available: see fulltext.
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