Supramolecular modification of ABC triblock terpolymers in confinement assembly

The self-assembly of AB diblock copolymers in three-dimensional (3D) soft confinement of nanoemulsions has recently become an attractive bottom up route to prepare colloids with controlled inner morphologies. In that regard, ABC triblock terpolymers show a more complex morphological behavior and could thus give access to extensive libraries of multicompartment microparticles. However, knowledge about their self-assembly in confinement is very limited thus far. Here, we investigated the confinement assembly of polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) (PS-b-P4VP-b-PT or SVT) triblock terpolymers in nanoemulsion droplets. Depending on the block weight fractions, we found spherical microparticles with concentric lamella–sphere (ls) morphology, i.e., PS/PT lamella intercalated with P4VP spheres, or unusual conic microparticles with concentric lamella–cylinder (lc) morphology. We further described how these morphologies can be modified through supramolecular additives, such as hydrogen bond (HB) and halogen bond (XB) donors. We bound donors to the 4VP units and analyzed changes in the morphology depending on the binding strength and the length of the alkyl tail. The interaction with the weaker donors resulted in an increase in volume of the P4VP domains, which depends upon the molar fraction of the added donor. For donors with a high tendency of intermolecular packing, a visible change in the morphology was observed. This ultimately caused a shape change in the microparticle. Knowledge about how to control inner morphologies of multicompartment microparticles could lead to novel carbon supports for catalysis, nanoparticles with unprecedented topologies, and potentially, reversible shape changes by light actuation

Ortho-Fluorination of azophenols increases the mesophase stability of photoresponsive hydrogen-bonded liquid crystals

Photoresponsive liquid crystals (LCs) whose alignment can be controlled with UV-Visible light are appealing for a range of photonic applications. From the perspective of exploring the interplay between the light response and the self-assembly of the molecular components, supramolecular liquid crystals are of particular interest. They allow elaborating the structure-property relationships that govern the optical performance of LC materials by subtle variation of the chemical structures of the building blocks. Herein we present a supramolecular system comprising azophenols and stilbazoles as hydrogen-bond donors and acceptors, respectively, and show that ortho-fluorination of the azophenol dramatically increases the thermal stability of the LC phases, an important characteristics in their further utilization in photonics. The systems exhibit fast photoinduced order-disorder transitions, and rapid recovery of the liquid-crystalline state once the light irradiation is ceased, due to the photochemical properties of azophenols

Effects of aging on identifying emotions conveyed by point-light walkers

M.G. was supported by EC FP7 HBP (grant 604102), PITN-GA-011-290011 (ABC) FP7-ICT-2013-10/ 611909 (KOROIBOT), and by GI 305/4-1 and KA 1258/15-1, and BMBF, FKZ: 01GQ1002A. K.S.P. was supported by a BBSRC New Investigator Grant. A.B.S. and P.J.B. were supported by an operating grant (528206) from the Canadian Institutes for Health Research. The authors also thank Donna Waxman for her valuable help in data collection for all experiments described here.Peer reviewedPostprin

A Tableaux Calculus for Reducing Proof Size

A tableau calculus is proposed, based on a compressed representation of clauses, where literals sharing a similar shape may be merged. The inferences applied on these literals are fused when possible, which reduces the size of the proof. It is shown that the obtained proof procedure is sound, refutationally complete and allows to reduce the size of the tableau by an exponential factor. The approach is compatible with all usual refinements of tableaux.Comment: Technical Repor

Cooling dynamics of a dilute gas of inelastic rods: a many particle simulation

We present results of simulations for a dilute gas of inelastically colliding particles. Collisions are modelled as a stochastic process, which on average decreases the translational energy (cooling), but allows for fluctuations in the transfer of energy to internal vibrations. We show that these fluctuations are strong enough to suppress inelastic collapse. This allows us to study large systems for long times in the truely inelastic regime. During the cooling stage we observe complex cluster dynamics, as large clusters of particles form, collide and merge or dissolve. Typical clusters are found to survive long enough to establish local equilibrium within a cluster, but not among different clusters. We extend the model to include net dissipation of energy by damping of the internal vibrations. Inelatic collapse is avoided also in this case but in contrast to the conservative system the translational energy decays according to the mean field scaling law, E(t)\propto t^{-2}, for asymptotically long times.Comment: 10 pages, 12 figures, Latex; extended discussion, accepted for publication in Phys. Rev.

High-resolution spectroscopy of triplet states of Rb2 by femtosecond pump-probe photoionization of doped helium nanodroplets

The dynamics of vibrational wave packets in triplet states of rubidium dimers (Rb2) formed on helium nanodroplets are studied using femtosecond pump-probe photoionization spectroscopy. Due to fast desorption of the excited Rb2 molecules off the droplets and due to their low internal temperature, wave packet oscillations can be followed up to very long pump-probe delay times >1.5ns. In the first excited triplet state (1)^3\Sigma_g^+, full and fractional revivals are observed with high contrast. Fourier analysis provides high-resolution vibrational spectra which are in excellent agreement with ab initio calculations

Depopulation of dense α-synuclein aggregates is associated with rescue of dopamine neuron dysfunction and death in a new Parkinson's disease model.

Parkinson's disease (PD) is characterized by the presence of α-synuclein aggregates known as Lewy bodies and Lewy neurites, whose formation is linked to disease development. The causal relation between α-synuclein aggregates and PD is not well understood. We generated a new transgenic mouse line (MI2) expressing human, aggregation-prone truncated 1-120 α-synuclein under the control of the tyrosine hydroxylase promoter. MI2 mice exhibit progressive aggregation of α-synuclein in dopaminergic neurons of the substantia nigra pars compacta and their striatal terminals. This is associated with a progressive reduction of striatal dopamine release, reduced striatal innervation and significant nigral dopaminergic nerve cell death starting from 6 and 12 months of age, respectively. In the MI2 mice, alterations in gait impairment can be detected by the DigiGait test from 9 months of age, while gross motor deficit was detected by rotarod test at 20 months of age when 50% of dopaminergic neurons in the substantia nigra pars compacta are lost. These changes were associated with an increase in the number and density of 20-500 nm α-synuclein species as shown by dSTORM. Treatment with the oligomer modulator anle138b, from 9 to 12 months of age, restored striatal dopamine release, prevented dopaminergic cell death and gait impairment. These effects were associated with a reduction of the inner density of large α-synuclein aggregates and an increase in dispersed small α-synuclein species as revealed by dSTORM. The MI2 mouse model recapitulates the progressive dopaminergic deficit observed in PD, showing that early synaptic dysfunction is associated to fine behavioral motor alterations, precedes dopaminergic axonal loss and neuronal death that become associated with a more consistent motor deficit upon reaching a certain threshold. Our data also provide new mechanistic insight for the effect of anle138b's function in vivo supporting that targeting α-synuclein aggregation is a promising therapeutic approach for PD