Stimulus-responsive block copolymer nano-objects and hydrogels via dynamic covalent chemistry

Herein we demonstrate that dynamic covalent chemistry can be used to induce reversible morphological transitions in block copolymer nano-objects and hydrogels. Poly(glycerol monomethacrylate)–poly(2- hydroxypropyl methacrylate) (PGMA–PHPMA) diblock copolymer nano-objects (vesicles or worms) were prepared via polymerization-induced self-assembly. Addition of 4-carboxyphenylboronic acid (CPBA) leads to the formation of phenylboronate ester bonds with the 1,2-diol pendent groups on the hydrophilic PGMA stabilizer chains; such binding causes a subtle reduction in the packing parameter, which in turn induces either vesicle-to-worm or worm-to-sphere transitions. Moreover, CPBA binding is pH-dependent, so reversible transitions can be achieved by switching the solution pH, with relatively high copolymer concentrations leading to associated (de)gelation. This distinguishes these new physical hydrogels from the covalently cross-linked gels prepared using dynamic covalent chemistry reported in the literature

Pareto optimality in house allocation problems

We study Pareto optimal matchings in the context of house allocation problems. We present an O(\sqrt{n}m) algorithm, based on Gales Top Trading Cycles Method, for finding a maximum cardinality Pareto optimal matching, where n is the number of agents and m is the total length of the preference lists. By contrast, we show that the problem of finding a minimum cardinality Pareto optimal matching is NP-hard, though approximable within a factor of 2. We then show that there exist Pareto optimal matchings of all sizes between a minimum and maximum cardinality Pareto optimal matching. Finally, we introduce the concept of a signature, which allows us to give a characterization, checkable in linear time, of instances that admit a unique Pareto optimal matching

Interactome network analysis identifies multiple caspase-6 interactors involved in the pathogenesis of HD

Caspase-6 (CASP6) has emerged as an important player in Huntington disease (HD), Alzheimer disease (AD) and cerebral ischemia, where it is activated early in the disease process. CASP6 also plays a key role in axonal degeneration, further underscoring the importance of this protease in neurodegenerative pathways. As a protein's function is modulated by its protein-protein interactions we performed a high throughput yeast-2-hybrid (Y2H) screen against ∼17,000 human proteins to gain further insight into the function of CASP6. We identified a high confidence list of 87 potential CASP6 interactors. From this list, 61% are predicted to contain a CASP6 recognition site. Of nine candidate substrates assessed, six are cleaved by CASP6. Proteins that did not contain a predicted CASP6 recognition site were assessed using a LUMIER assay approach and 51% were further validated as interactors by this method. Of note, 54% of the high-confidence interactors identified show alterations in human HD brain at the mRNA level, and there is a significant enrichment for previously validated huntingtin (HTT) interactors. One protein of interest, STK3, a proapoptotic kinase, was validated biochemically to be a CASP6 substrate. Furthermore, our results demonstrate that in striatal cells expressing mutant huntingtin (mHTT) an increase in full length and fragment levels of STK3 are observed. We further show that caspase-3 is not essential for the endogenous cleavage of STK3. Characterization of the interaction network provides important new information regarding key pathways of interactors of CASP6 and highlights potential novel therapeutic targets for HD, AD and cerebral ischemia

Using Host-Guest Chemistry to Tune the Kinetics of Morphological Transitions Undertaken by Block Copolymer Vesicles

Host-guest chemistry is exploited to tune the rate at which block copolymer vesicles undergo morphological transitions. More specifically, a concentrated aqueous dispersion of poly(glycerol monomethacrylate-co-glycidyl methacrylate)-poly(2-hydroxypropyl methacrylate) [P(GMA-co-GlyMA)-PHPMA] diblock copolymer vesicles was prepared via polymerization-induced self-assembly (PISA). The epoxy groups in the GlyMA residues were ring-opened using a primary amine-functionalized β-cyclodextrin (NH 2 -β-CD) in order to prepare β-CD-decorated vesicles. Addition of azobenzene-methoxypoly(ethylene glycol) (azo-mPEG) to such vesicles results in specific binding of this water-soluble macromolecular reagent to the β-CD groups on the hydrophilic P(GMA-co-GlyMA) stabilizer chains. Such host-guest chemistry induces a morphological transition from vesicles to worms and/or spheres. Furthermore, the rate of this morphological transition can be tuned by UV/visible-light irradiation and/or guest molecule competition. This novel molecular recognition strategy offers considerable scope for the design of new stimulus-responsive diblock copolymer vesicles for targeted delivery and controlled release of cargoes

Ammonium cations with high pK a in perovskite solar cells for improved high-temperature photostability

Phenethylammonium (PEA+) and butylammonium (BA+) are widely used in three-dimensional (3D) perovskites to form two-dimensional perovskites at film surfaces and grain boundaries (GBs) for defect passivation and performance enhancement. Here we show that these cations are unstable with 3D formamidinium (FA+)-containing perovskites under high-temperature light soaking. PEA+ and BA+ are found to deprotonate to amines, which then react with FA+ to produce (phenethylamino)methaniminium (PEAMA+) and (butylamino)methaniminium (BAMA+), respectively, severely limiting device high-temperature photostability. Removing these cations greatly improves the photostability but compromises device efficiency by leaving non-fully passivated surfaces and GBs. Ammonium cations with a high acid dissociation constant (pK a), including PEAMA+ (pK a = 12.0) and BAMA+ (pK a = 12.0), can replace PEA+ or BA+ for passivation and are stable with FA-based perovskites due to their resistance to further deprotonation. P–i–n structure solar cells with PEAMA+ additive maintained over 90% of their initial efficiency after light soaking at open circuit and 90 °C for 1,500 hours

Search for Invisible Decays of η\eta and η′\eta^\prime in J/ψ→ϕηJ/\psi \to \phi\eta and ϕη′\phi \eta^\prime

Using a data sample of $58\times 10^6$ $J/\psi$ decays collected with the BES II detector at the BEPC, searches for invisible decays of $\eta$ and $\eta^\prime$ in $J/\psi$ to $\phi\eta$ and $\phi\eta^\prime$ are performed. The $\phi$ signals, which are reconstructed in $K^+K^-$ final states, are used to tag the $\eta$ and $\eta^\prime$ decays. No signals are found for the invisible decays of either $\eta$ or $\eta^\prime$, and upper limits at the 90% confidence level are determined to be $1.65 \times 10^{-3}$ for the ratio $\frac{B(\eta\to \text{invisible})}{B(\eta\to\gamma\gamma)}$ and $6.69\times 10^{-2}$ for $\frac{B(\eta^\prime\to \text{invisible})}{B(\eta^\prime\to\gamma\gamma)}$. These are the first searches for $\eta$ and $\eta^\prime$ decays into invisible final states.Comment: 5 pages, 4 figures; Added references, Corrected typo

Observation of Two New N* Peaks in J/psi -> ppi−nˉp pi^- \bar n and pˉπ+n\bar p\pi^+n Decays

The $\pi N$ system in decays of $J/\psi\to\bar NN\pi$ is limited to be isospin 1/2 by isospin conservation. This provides a big advantage in studying $N^*\to \pi N$ compared with $\pi N$ and $\gamma N$ experiments which mix isospin 1/2 and 3/2 for the $\pi N$ system. Using 58 million $J/\psi$ decays collected with the Beijing Electron Positron Collider, more than 100 thousand $J/\psi \to p \pi^- \bar n + c.c.$ events are obtained. Besides two well known $N^*$ peaks at 1500 MeV and 1670 MeV, there are two new, clear $N^*$ peaks in the $p\pi$ invariant mass spectrum around 1360 MeV and 2030 MeV. They are the first direct observation of the $N^*(1440)$ peak and a long-sought "missing" $N^*$ peak above 2 GeV in the $\pi N$ invariant mass spectrum. A simple Breit-Wigner fit gives the mass and width for the $N^*(1440)$ peak as $1358\pm 6 \pm 16$ MeV and $179\pm 26\pm 50$ MeV, and for the new $N^*$ peak above 2 GeV as $2068\pm 3^{+15}_{-40}$ MeV and $165\pm 14\pm 40$ MeV, respectively

Search for the Rare Decays J/Psi --> Ds- e+ nu_e, J/Psi --> D- e+ nu_e, and J/Psi --> D0bar e+ e-

We report on a search for the decays J/Psi --> Ds- e+ nu_e + c.c., J/Psi --> D- e+ nu_e + c.c., and J/Psi --> D0bar e+ e- + c.c. in a sample of 5.8 * 10^7 J/Psi events collected with the BESII detector at the BEPC. No excess of signal above background is observed, and 90% confidence level upper limits on the branching fractions are set: B(J/Psi --> Ds- e+ nu_e + c.c.)<4.8*10^-5, B(J/Psi --> D- e+ nu_e + c.c.) D0bar e+ e- + c.c.)<1.1*10^-5Comment: 10 pages, 4 figure