Fluctuation effects in the theory of microphase separation of diblock copolymers in the presence of an electric field

We generalize the Fredrickson-Helfand theory of the microphase separation in symmetric diblock copolymer melts by taking into account the influence of a time-independent homogeneous electric field on the composition fluctuations within the self-consistent Hartree approximation. We predict that electric fields suppress composition fluctuations, and consequently weaken the first-order transition. In the presence of an electric field the critical temperature of the order-disorder transition is shifted towards its mean-field value. The collective structure factor in the disordered phase becomes anisotropic in the presence of the electric field. Fluctuational modulations of the order parameter along the field direction are strongest suppressed. The latter is in accordance with the parallel orientation of the lamellae in the ordered state.Comment: 16 page

Gyroid Optical Metamaterials: Calculating the Effective Permittivity of Multidomain Samples

Gold gyroid optical metamaterials are known to possess a reduced plasma frequency and linear dichroism imparted by their intricate subwavelength single gyroid morphology. The anisotropic optical properties are, however, only evident when a large individual gyroid domain is investigated. Multidomain gyroid metamaterials, fabricated using a polyisoprene-$b$-polystyrene-$b$-poly(ethylene oxide) triblock terpolymer and consisting of multiple small gyroid domains with random orientation and handedness, instead exhibit isotropic optical properties. Comparing three effective medium models, we here show that the specular reflectance spectra of such multidomain gyroid optical metamaterials can be accurately modeled over a broad range of incident angles by a Bruggeman effective medium consisting of a random wire array. This model accurately reproduces previously published results tracking the variation in normal incidence reflectance spectra of gold gyroid optical metamaterials as a function of host refractive index and volume fill fraction of gold. The effective permittivity derived from this theory confirms the change in sign of the real part of the permittivity in the visible spectral region (so, that gold gyroid metamaterials exhibit both dielectric and metallic behavior at optical wavelengths). That a Bruggeman effective medium can accurately model the experimental reflectance spectra implies that small multidomain gold gyroid optical metamaterials behave both qualitatively and quantitatively as an amorphous composite of gold and air (i.e., nanoporous gold) and that coherent electromagnetic contributions arising from the subwavelength gyroid symmetry are not dominant.This research was supported through the Swiss National Science Foundation through the National Center of Competence in Research Bio-Inspired Materials and grant numbers 200021_163220 (to U.S.) and PZ00P2_168223 (to B.D.W.), the Adolphe Merkle Foundation, the Engineering and Physical Sciences Research Council (EPSRC) through the Cambridge NanoDTC EP/G037221/1, EP/L027151/1, and EP/ G060649/1, and ERC LINASS 320503 and from the European Union’s Horizon 2020 Research and Innovation Programme under the Marie Sklodowska-Curie grant agreement no. 706329 (to I.G.). Y.G. and U.W. thank the National Science Foundation (DMR-1409105) for financial support

Identifying Ionic and Electronic Charge Transfer at Oxide Heterointerfaces

The ability to tailor oxide heterointerfaces has led to novel properties in low-dimensional oxide systems. A fundamental understanding of these properties is based on the concept of electronic charge transfer. However, the electronic properties of oxide heterointerfaces crucially depend on their ionic constitution and defect structure: ionic charges contribute to charge transfer and screening at oxide interfaces, triggering a thermodynamic balance of ionic and electronic structures. Quantitative understanding of the electronic and ionic roles regarding charge-transfer phenomena poses a central challenge. Here, the electronic and ionic structure is simultaneously investigated at the prototypical charge-transfer heterointerface, LaAlO3/SrTiO3. Applying in situ photoemission spectroscopy under oxygen ambient, ionic and electronic charge transfer is deconvoluted in response to the oxygen atmosphere at elevated temperatures. In this way, both the rich and variable chemistry of complex oxides and the associated electronic properties are equally embraced. The interfacial electron gas is depleted through an ionic rearrangement in the strontium cation sublattice when oxygen is applied, resulting in an inverse and reversible balance between cation vacancies and electrons, while the mobility of ionic species is found to be considerably enhanced as compared to the bulk. Triggered by these ionic phenomena, the electronic transport and magnetic signature of the heterointerface are significantly altered

Polymer-templated mesoporous lithium titanate microspheres for high-performance lithium batteries

The spinel Li4Ti5O12 (LTO) is a promising lithium ion battery anode material with the potential to supplement graphite as an industry standard, but its low electrical conductivity and Li–ion diffusivity need to be overcome. Here, mesoporous LTO microspheres with carbon-coatings were formed by phase separation of a homopolymer from microphase-separated block copolymers of varying molar masses containing sol–gel precursors. Upon heating the composite underwent a sol–gel condensation reaction followed by the eventual pyrolysis of the polymer templates. The optimised mesoporous LTO microspheres demonstrated an excellent electrochemical performance with an excellent specific discharge capacity of 164 mA h g−1, 95% of which was retained after 1000 cycles at a C-rate of 10

How AI Systems Challenge the Conditions of Moral Agency?

The article explores the effects increasing automation has on our conceptions of human agency. We conceptualize the central features of human agency as ableness, intentionality, and rationality and define responsibility as a central feature of moral agency. We discuss suggestions in favor of holding AI systems moral agents for their functions but join those who refute this view. We consider the possibility of assigning moral agency to automated AI systems in settings of machine-human cooperation but come to the conclusion that AI systems are not genuine participants in joint action and cannot be held morally responsible. Philosophical issues notwithstanding, the functions of AI systems change human agency as they affect our goal setting and pursuing by influencing our conceptions of the attainable. Recommendation algorithms on news sites, social media platforms, and in search engines modify our possibilities to receive accurate and comprehensive information, hence influencing our decision making. Sophisticated AI systems replace human workforce even in such demanding fields as medical surgery, language translation, visual arts, and composing music. Being second to a machine in an increasing number of fields of expertise will affect how human beings regard their own abilities. We need a deeper understanding of how technological progress takes place and how it is intertwined with economic and political realities. Moral responsibility remains a human characteristic. It is our duty to develop AI to serve morally good ends and purposes. Protecting and strengthening the conditions of human agency in any AI environment is part of this task.Peer reviewe

Conviviality and Parallax in David Olusoga’s Black and British: A Forgotten History

Through examining the BBC television series, Black and British: A Forgotten History, written and presented by the historian David Olusoga, and in extending Paul Gilroy’s assertion that the everyday, banality of living with difference is now an ordinary part of British life, this article considers how Olusoga’s historicization of the black British experience reflects a convivial rendering of UK multiculture. In particular, when used alongside Žižek’s notion of parallax, it is argued that understandings of convivial culture can be supported by a historical importance that deliberately ‘shocks’ and, subsequently dislodges, popular interpretations of the UK’s ‘white past’. Notably, it is parallax which puts antagonism, strangeness and ambivalence at the heart of contemporary depictions of convivial Britain, with the UK’s cultural differences located in the ‘gaps’ and tensions which characterize both its past and present. These differences should not be feared but, as a characteristic part of our convivial culture, should be supplemented with historical analyses that highlight but, also, undermine, the significance of cultural differences in the present. Consequently, it is suggested that if the spontaneity of conviviality is to encourage openness, then, understandings of multiculturalism need to go beyond reification in order to challenge our understandings of the past. Here, examples of ‘alterity’ are neither ‘new’ nor ‘contemporary’ but, instead, constitute a fundamental part of the nation’s history: of the ‘gap’ made visible in transiting past and present

4D Super-Resolution Microscopy with Conventional Fluorophores and Single Wavelength Excitation in Optically Thick Cells and Tissues

Optical super-resolution imaging of fluorescently stained biological samples is rapidly becoming an important tool to investigate protein distribution at the molecular scale. It is therefore important to develop practical super-resolution methods that allow capturing the full three-dimensional nature of biological systems and also can visualize multiple protein species in the same sample

MLP (muscle LIM protein) as a stress sensor in the heart

Muscle LIM protein (MLP, also known as cysteine rich protein 3 (CSRP3, CRP3)) is a muscle-specific-expressed LIM-only protein. It consists of 194 amino-acids and has been described initially as a factor involved in myogenesis (Arber et al. Cell 79:221–231, 1994). MLP soon became an important model for experimental cardiology when it was first demonstrated that MLP deficiency leads to myocardial hypertrophy followed by a dilated cardiomyopathy and heart failure phenotype (Arber et al. Cell 88:393–403, 1997). At this time, this was the first genetically altered animal model to develop this devastating disease. Interestingly, MLP was also found to be down-regulated in humans with heart failure (Zolk et al. Circulation 101:2674–2677, 2000) and MLP mutations are able to cause hypertrophic and dilated forms of cardiomyopathy in humans (Bos et al. Mol Genet Metab 88:78–85, 2006; Geier et al. Circulation 107:1390–1395, 2003; Hershberger et al. Clin Transl Sci 1:21–26, 2008; Knöll et al. Cell 111:943–955, 2002; Knöll et al. Circ Res 106:695–704, 2010; Mohapatra et al. Mol Genet Metab 80:207–215, 2003). Although considerable efforts have been undertaken to unravel the underlying molecular mechanisms—how MLP mutations, either in model organisms or in the human setting cause these diseases are still unclear. In contrast, only precise knowledge of the underlying molecular mechanisms will allow the development of novel and innovative therapeutic strategies to combat this otherwise lethal condition. The focus of this review will be on the function of MLP in cardiac mechanosensation and we shall point to possible future directions in MLP research

Hydrophobically Modified Sulfobetaine Copolymers with Tunable Aqueous UCST through Postpolymerization Modification of Poly(pentafluorophenyl acrylate)

Polysulfobetaines, polymers carrying highly polar zwitterionic side chains, present a promising research field by virtue of their antifouling properties, hemocompatibility, and stimulus-responsive behavior. However, limited synthetic approaches exist to produce sulfobetaine copolymers comprising hydrophobic components. Postpolymerization modification of an activated ester precursor, poly(pentafluorophenyl acrylate), employing a zwitterionic amine, 3-((3-aminopropyl)dimethylammonio)propane-1-sulfonate, ADPS, is presented as a novel, one-step synthetic concept toward sulfobetaine (co)polymers. Modifications were performed in homogeneous solution using propylene carbonate as solvent with mixtures of ADPS and pentylamine, benzylamine, and dodecylamine producing a series of well-defined statistical acrylamido sulfobetaine copolymers containing hydrophobic pentyl, benzyl, or dodecylacrylamide comonomers with well-controllable molar composition as evidenced by NMR and FT-IR spectroscopy and size exclusion chromatography.This synthetic strategy was exploited to investigate, for the first time, the influence of hydrophobic modification on the upper critical solution temperature (UCST) of sulfobetaine copolymers in aqueous solution. Surprisingly, incorporation of pentyl groups was found to increase solubility over a wide composition range, whereas benzyl groups decreased solubility—an effect attributed to different entropic and enthalpic contributions of both functional groups. While UCST transitions of polysulfobetaines are typically limited to higher molar mass samples, incorporation of 0–65 mol % of benzyl groups into copolymers with molar masses of 25.5–34.5 kg/mol enabled sharp, reversible transitions from 6 to 82 °C in solutions containing up to 76 mM NaCl, as observed by optical transmittance and dynamic light scattering. Both synthesis and systematic UCST increase of sulfobetaine copolymers presented here are expected to expand the scope and applicability of these smart materials