Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers

Multiblock copolymers (MBCPs) are an emerging class of materials that are becoming more accessible in recent years. However, to date there is still a lack of fundamental understanding of their physical properties. In particular, the glass transition temperature (Tg) which is known to be affected by the phase separation has not been well characterized experimentally. To this end, we report the first experimental study on the evolution of the Tgs and the corresponding phase separation of linear MBCPs with increasing number of blocks while keeping the overall degree of polymerization (DP) constant (DP = 200). Ethylene glycol methyl ether acrylate (EGMEA) and tert-butyl acrylate (tBA) were chosen as monomers for reversible addition-fragmentation chain transfer polymerization to synthesize MBCPs. We found the Tgs (as measured by differential scanning calorimetry) of EGMEA and tBA segments within the MCBPs to converge with increasing number of blocks and decreasing block length, correlating with the loss of the heterogeneity as observed from small-angle X-ray scattering (SAXS) analysis. The Tgs of the multiblock copolymers were also compared to the Tgs of the polymer blends of the corresponding homopolymers, and we found that Tgs of the polymer blends were similar to those of the respective homopolymers, as expected. SAXS experiments further demonstrated microphase separation of multiblock copolymers. This work demonstrates the enormous potential of multiblock architectures to tune the physical properties of synthetic polymers, by changing their glass transition temperature and their morphologies obtained from microphase separation, with domain sizes reaching under 10 nm

Antimatter and Matter Production in Heavy Ion Collisions at CERN (The NEWMASS Experiment NA52)

Besides the dedicated search for strangelets NA52 measures light (anti)particle and (anti)nuclei production over a wide range of rapidity. Compared to previous runs the statistics has been increased in the 1998 run by more than one order of magnitude for negatively charged objects at different spectrometer rigidities. Together with previous data taking at a rigidity of -20 GeV/c we obtained 10^6 antiprotons 10^3 antideuterons and two antihelium3 without centrality requirements. We measured nuclei and antinuclei (p,d,antiprotons, antideuterons) near midrapidity covering an impact parameter range of b=2-12 fm. Our results strongly indicate that nuclei and antinuclei are mainly produced via the coalescence mechanism. However the centrality dependence of the antibaryon to baryon ratios show that antibaryons are diminished due to annihilation and breakup reactions in the hadron dense environment. The volume of the particle source extracted from coalescence models agrees with results from pion interferometry for an expanding source. The chemical and thermal freeze-out of nuclei and antinuclei appear to coincide with each other and with the thermal freeze-out of hadrons.Comment: 12 pages, 8 figures, to appear in the proceedings of the conference on 'Fundamental Issues in Elementary Matter' Bad Honnef, Germany, Sept. 25-29, 200

Open Problems on Central Simple Algebras

We provide a survey of past research and a list of open problems regarding central simple algebras and the Brauer group over a field, intended both for experts and for beginners.Comment: v2 has some small revisions to the text. Some items are re-numbered, compared to v

Contributions of hard and soft blocks in the self-healing of metal-ligand-containing block copolymers

The main aim of this work is to study the respective contribution of the hard and soft blocks of a metal-ligand containing block copolymer to the self-healing behavior. To this aim, different block copolymers containing terpyridine were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. These block copolymers consisted of polystyrene as the hard block, n-butyl acrylate (BA) as soft block and terpyridine units as the ligand moiety placed at different locations in the soft block. These block copolymers were complexed with manganese(II) chloride to introduce transient crosslinks and, thus, self-healing behavior. Homopolymers with the hard and soft block only were also synthesized and tested. A quasi-irreversible crosslinking, i.e. by using nickel(II) nitrate, was performed in order to study the dynamics of the permanently (strongly) crosslinked network. Rheological master curves were generated enabling the determination of the terminal flow in these networks and the reversibility of the supramolecular interactions. Additionally, the macroscopic scratch healing behavior and the molecular mobility of the polymer chains in these supramolecular networks were investigated. A kinetic study of the scratch healing was performed to determine the similarities in temperature dependence for rheological relaxations and macroscopic scratch healing. In our previous work, we have explored the effect of strength of the reversible metal-ligand interaction and the effect of changing the ratio of hard to soft block. This work goes further in separating the individual contributions of the hard and soft blocks as well as the reversible interactions and to reveal their relative importance in the complex phenomenon of scratch healing

Mesoporous monoliths of inverse bicontinuous cubic phases of block copolymer bilayers

Solution self-assembly of block copolymers into inverse bicontinuous cubic mesophases is a promising new approach for creating porous polymer films and monoliths with highly organized bicontinuous mesoporous networks. Here we report the direct self-assembly of block copolymers with branched hydrophilic blocks into large monoliths consisting of the inverse bicontinuous cubic structures of the block copolymer bilayer. We suggest a facile and scalable method of solution self-assembly by diffusion of water to the block copolymer solution, which results in the unperturbed formation of mesoporous monoliths with large-pore (>25nm diameter) networks weaved in crystalline lattices. The surface functional groups of the internal large-pore networks are freely accessible for large guest molecules such as protein complexes of which the molecular weight exceeded 100kDa. The internal double-diamond (Pn3m) networks of large pores within the mesoporous monoliths could be replicated to self-supporting three-dimensional skeletal structures of crystalline titania and mesoporous silica.open2

MicroRNA networks direct neuronal development and plasticity

MicroRNAs (miRNAs) constitute a class of small, non-coding RNAs that act as post-transcriptional regulators of gene expression. In neurons, the functions of individual miRNAs are just beginning to emerge, and recent studies have elucidated roles for neural miRNAs at various stages of neuronal development and maturation, including neurite outgrowth, dendritogenesis, and spine formation. Notably, miRNAs regulate mRNA translation locally in the axosomal and synaptodendritic compartments, and thereby contribute to the dynamic spatial organization of axonal and dendritic structures and their function. Given the critical role for miRNAs in regulating early brain development and in mediating synaptic plasticity later in life, it is tempting to speculate that the pathology of neurological disorders is affected by altered expression or functioning of miRNAs. Here we provide an overview of recently identified mechanisms of neuronal development and plasticity involving miRNAs, and the consequences of miRNA dysregulation

Detection of π+π−\pi^+\pi^-atoms with the DIRAC spectrometer at CERN

The goal of the DIRAC experiment at CERN is to measure with high precision the lifetime of the $\pi^+\pi^-$ atom ($A_{2\pi}$), which is of order $3\times10^{-15}$ s, and thus to determine the s-wave $\pi\pi$-scattering lengths difference $|a_{0}-a_{2}|$. $A_{2\pi}$ atoms are detected through the characteristic features of $\pi^+\pi^-$ pairs from the atom break-up (ionization) in the target. We report on a first high statistics atomic data sample obtained from p Ni interactions at 24 GeV/$c$ proton momentum and present the methods to separate the signal from the background.Comment: 19 pages, 12 figures, 1 tabl

Mesostructured Block Copolymer Nanoparticles: Versatile Templates for Hybrid Inorganic/Organic Nanostructures

We present a versatile strategy to prepare a range of nanostructured poly(styrene)-block-poly(2-vinyl pyridine) copolymer particles with tunable interior morphology and controlled size by a simple solvent exchange procedure. A key feature of this strategy is the use of functional block copolymers incorporating reactive pyridyl moieties which allow the absorption of metal salts and other inorganic precursors to be directed. Upon reduction of the metal salts, well-defined hybrid metal nanoparticle arrays could be prepared, whereas the use of oxide precursors followed by calcination permits the synthesis of silica and titania particles. In both cases, ordered morphologies templated by the original block copolymer domains were obtained