In Situ Synthesis and Characterization of Poly(aryleneethynylene)‐Grafted Reduced Graphene Oxide

Using highly soluble bromo‐functionalized reduced graphene oxide (RGBr) as a key graphene template for surface‐directing Sonogashira–Hagihara polymerization, a novel soluble poly(arylene‐ethynylene)‐grafted reduced graphene oxide, hereafter abbreviated as PAE‐g‐RGO, was prepared in situ. The entirely different electron distribution of LUMO and HOMO of PAE‐g‐RGO suggested the existence of a charge‐transfer (CT) state (PAE^.?–RGO^.+). The negative ΔG_CS value (?2.57 eV) indicates that the occurrence of the charge separation via ¹RGO* in o‐DCB is exothermic and favorable. Upon irradiation with 365 nm light, the light‐induced electron paramagnetic resonance (LEPR) spectrum of PAE‐g‐RGO showed a decrease in the spin‐state density owing to photoinduced intramolecular electron transfer events in this system. A sandwich‐type Al/PAE‐g‐RGO/ITO device showed representative bistable electrical switching behavior. The nonvolatile memory performance was attributed to the CT‐induced conductance changes, which was supported by molecular computation results and conductive atomic force microscopy (C‐AFM) images.     

LWE from non-commutative group rings

Designs, Codes and Cryptography - The Learning-With-Errors (LWE) problem (and its variants including Ring-LWE and Module-LWE), whose security are based on hard ideal lattice problems, has proven to...     

Hydrogen‐Bonded Films for Zero‐Order Release of Leuprolide

Leuprolide has been widely used in androgen deprivation therapy for the treatment of advanced prostate cancer, but its use is still limited due to its short half‐life. Herein, hydrogen‐bonded layer‐by‐layer films are fabricated from PEGylated leuprolide (PEG‐LEU) and tannic acid (TA). Because of its dynamic nature, the film disintegrates gradually in water and releases PEG‐LEU and TA. The in vitro release profile indicated perfect zero‐order kinetics, which is explained by the unique release mechanism. When implanted subcutaneously in male rats, the films maintain a constant serum drug level. For a 60‐bilayer film, the serum drug level is maintained constant for ≈24 days. No initial burst release is observed, suggesting that the in vivo release also follows zero‐order kinetics. Initially, an increase in the level of serum testosterone is induced by the released drug, followed by testosterone suppression to a constant level below the castrate level, which could be maintained as long as a constant serum drug level is maintained. Since the new drug carriers avoid an initial burst release of the drug and maintain a constant serum drug level and hence a constant serum testosterone level below the castrate level, these carriers are highly promising for androgen deprivation therapy.     

Enantioselective Synthesis of a Chiral Coordination Polymer with Circularly Polarized Visible Laser

Circular dichroism is known to be the feature of a chiral agent which has inspired scientist to study the interesting phenomena of circularly polarized light (CPL) modulated molecular chirality. Although several organic molecules or assemblies have been found to be CPL‐responsive, the influence of CPL on the assembly of chiral coordination compounds remains unknown. Herein, a chiral coordination polymer, which is constructed from achiral agents, was used to study the CPL‐induced enantioselective synthesis. By irradiation with either left‐handed or right‐handed CPL during the reaction and crystallization, enantiomeric excesses of the crystalline product were obtained. Left‐handed CPL resulted in crystals with a left‐handed helical structure, and right‐handed CPL led to crystals with a right‐handed helical structure. It is exciting that the absolute asymmetric synthesis of a chiral coordination polymer could be enantioselective when using CPL, and provides a strategy for the control of the chirality of chiral coordination polymers.     

Self-Assembly Approach Towards MoS2-Embedded Hierarchical Porous Carbons for Enhanced Electrocatalytic Hydrogen Evolution

Transition metal-based nanoparticle-embedded carbon materials have received increasing attention for constructing next-generation electrochemical catalysts for energy storage and conversion. However, designing hybrid carbon materials with controllable hierarchical micro/mesoporous structures, excellent dispersion of metal nanoparticles, and multiple heteroatom-doping remains challenging. Here, a novel pyridinium-containing ionic hypercrosslinked micellar frameworks (IHMFs) prepared from the core–shell unimicelle of s-poly(tert-butyl acrylate)-b-poly(4-bromomethyl) styrene (s-PtBA-b-PBMS) and linear poly(4-vinylpyridine) were used as self-sacrificial templates for confined growth of molybdenum disulfide (MoS₂) inside cationic IHMFs through electrostatic interaction. After pyrolysis, MoS₂-anchored nitrogen-doped porous carbons possessing tunable hierarchical micro/mesoporous structures and favorable distributions of MoS₂ nanoparticles exhibited excellent electrocatalytic activity for hydrogen evolution reaction as well as small Tafel slope of 66.7 mV dec⁻¹, low onset potential, and excellent cycling stability under acidic condition. Crucially, hierarchical micro/mesoporous structure and high surface area could boost their catalytic hydrogen evolution performance. This approach provides a novel route for preparation of micro/mesoporous hybrid carbon materials with confined transition metal nanoparticles for electrochemical energy conversion.     

Static Retention of Dynamic Chiral Arrangements for Achiral Shear Thinning Metal–Organic Colloids

Chiral compounds are known to be important not only because they are the fundamental components of living organisms, but also for their unique chiroptical properties. In recent years, scientists have fabricated several chiral organic supramolecular aggregates by using chiral physical fields, such as vortex flow. Herein, the relationship between dynamic chiroptical properties and rheological nature is discussed, suggesting the shear thinning properties of non-Newtonian fluids might help colloidal particles adopt a chiral arrangement in vortices. Furthermore, the storage modulus of colloids could be increased by adding a linking agent, which successfully kept the dynamic chiroptical properties in the static state. Moreover, the salt effect on the host–guest interaction involved in the colloids was studied, the results suggested a significant enhancement of the transferred dynamic circular dichroism for the achiral guest molecule.     

Intermetallic Pt2Si：magnetron-sputtering preparation and electrocatalysis toward ethanol oxidation

Although most transition metals have been tested as the promoter to Pt for electrocatalysis toward fuel cell reactions,semi-conductor elements,such as Si,have hitherto not been examined.Here we report a simple synthesis of intermetallic Pt2Si electrode using magnetron sputtering and the electrocatalysis toward ethanol oxidation reaction（EOR）.In comparison to Pt,the intermetallic Pt2Si surface turns out to be much more active in catalyzing the EOR：the onset potential shifts negatively by 150 mV,and the current density at 0.6 V increases by a magnitude of one order.Such an enormous enhancement in EOR catalysis is ascribed to the promotion effects of Si,which can not only provide active surface oxygenated species to accelerate the removal of COads,but also strongly alter the electronic property of Pt,as clearly indicated by the core-level shift in XPS spectrum.     

The Structural Fate of Individual Multicomponent Metal‐Oxide Nanoparticles in Polymer Nanoreactors

Multicomponent nanoparticles can be synthesized with either homogeneous or phase‐segregated architectures depending on the synthesis conditions and elements incorporated. To understand the parameters that determine their structural fate, multicomponent metal‐oxide nanoparticles consisting of combinations of Co, Ni, and Cu were synthesized by using scanning probe block copolymer lithography and characterized using correlated electron microscopy. These studies revealed that the miscibility, ratio of the metallic components, and the synthesis temperature determine the crystal structure and architecture of the nanoparticles. A Co‐Ni‐O system forms a rock salt structure largely owing to the miscibility of CoO and NiO, while Cu‐Ni‐O, which has large miscibility gaps, forms either homogeneous oxides, heterojunctions, or alloys depending on the annealing temperature and composition. Moreover, a higher‐ordered structure, Co‐Ni‐Cu‐O, was found to follow the behavior of lower ordered systems.