Aqueous electrochemically-triggered atom transfer radical polymerization

Simplified electrochemical atom transfer radical polymerization (seATRP) using Cu^II–N-propyl pyridineimine complexes (Cu^II(NPPI)₂) is reported for the first time. In aqueous solution, using oligo(ethylene glycol) methyl ether methacrylate (OEGMA), standard electrolysis conditions yield POEGMA with good control over molecular weight distribution (Đ_m < 1.35). Interestingly, the polymerizations are not under complete electrochemical control, as monomer conversion continues when electrolysis is halted. Alternatively, it is shown that the extent and rate of polymerization depends upon an initial period of electrolysis. Thus, it is proposed that seATRP using Cu^II(NPPI)₂ follows an electrochemically-triggered, rather than electrochemically mediated, ATRP mechanism, which distinguishes them from other Cu^IIL complexes that have been previously reported in the literature.

Simplified electrochemical atom transfer radical polymerization (seATRP) using Cu^II-pyridineimine complexes is reported and follows a previously unreported electrochemically triggered mechanism.     

Molten-Salt-Mediated Synthesis of an Atomic Nickel Co-catalyst on TiO2 for Improved Photocatalytic H2 Evolution

Atomic co-catalysts offer high potential to improve the photocatalytic performance, of which the preparation with earth-abundant elements is challenging. Here, a new molten salt method (MSM) is designed to prepare atomic Ni co-catalyst on widely studied TiO₂ nanoparticles. The liquid environment and space confinement effect of the molten salt leads to atomic dispersion of Ni ions on TiO₂, while the strong polarizing force provided by the molten salt promotes formation of strong Ni−O bonds. Interestingly, Ni atoms are found to facilitate the formation of oxygen vacancies (OV) on TiO₂ during the MSM process, which benefits the charge transfer and hydrogen evolution reaction. The synergy of atomic Ni co-catalyst and OV results in 4-time increase in H₂ evolution rate compared to that of the Ni co-catalyst on TiO₂ prepared by an impregnation method. This work provides a new strategy of controlling atomic co-catalyst together with defects for efficient photocatalytic water splitting.     

Grain size engineering and growth mechanism in hydrothermal synthesis of Bi0.5Na0.5TiO3 thin films on Nb-doped SrTiO3 substrates

Journal of Sol-Gel Science and Technology - Considering the full utilization of energy and pursuing thin-film capacitors with high energy-storage density, the grain size engineering is used to...     

Finite particle number description of neutron matter using the unitary correlation operator and high-momentum pair methods

Using bare Argonne V4' (AV4'), V6' (AV6'), and V8' (AV8') nucleon–nucleon (\begin{document}$NN$\end{document}) interactions, the nuclear equations of state (EOSs) for neutron matter are calculated with the unitary correlation operator and high-momentum pair methods. Neutron matter is described using a finite particle number approach with magic number \begin{document}$N=66$\end{document} under a periodic boundary condition. The central short-range correlation originating from the short-range repulsion in the \begin{document}$NN$\end{document} interaction is treated by the unitary correlation operator method (UCOM), and the tensor correlation and spin-orbit effects are described by the two-particle two-hole (2p2h) excitations of nucleon pairs, where the two nucleons with a large relative momentum are regarded as a high-momentum (HM) pair. With increasing 2p2h configurations, the total energy per particle of the neutron matter is well-converged under this UCOM+HM framework. Comparing the results calculated with AV4', AV6', and AV8' \begin{document}$NN$\end{document} interactions, we demonstrate the effects of the short-range correlation, tensor correlation, and spin-orbit coupling on the density dependence of the total energy per particle of neutron matter. Moreover, the contribution of each Hamiltonian component to the total energy per particle is discussed. The EOSs of neutron matter calculated within the present UCOM+HM framework agree with the calculations of six microscopic many-body theories, especially the auxiliary field-diffusion Monte Carlo calculations.     

Fused-ring electron acceptors in China

正In recent years, organic photovoltaics (OPVs) as one of nextgeneration solar energy technologies have attracted intense interest since they are featured with low cost, light weight,flexibility and semi-transparency [1]. At the early stage in the OPV field, fullerenes and their derivatives dominated electron acceptor materials due to their high electron affinity,high electron mobility and isotropic electron transporting ability, and fullerene-based devices yielded power conversion efficiencies (PCEs) up to～12%[2].     

Strain-Enhanced Metallic Intermixing in Shape-Controlled Multilayered Core–Shell Nanostructures: Toward Shaped Intermetallics

Controlling the surface composition of shaped bimetallic nanoparticles could offer precise tunability of geometric and electronic surface structure for new nanocatalysts. To achieve this goal, a platform for studying the intermixing process in a shaped nanoparticle was designed, using multilayered Pd-Ni-Pt core–shell nanocubes as precursors. Under mild conditions, the intermixing between Ni and Pt could be tuned by changing layer thickness and number, triggering intermixing while preserving nanoparticle shape. Intermixing of the two metals is monitored using transmission electron microscopy. The surface structure evolution is characterized using electrochemical methanol oxidation. DFT calculations suggest that the low-temperature mixing is enhanced by shorter diffusion lengths and strain introduced by the layered structure. The platform and insights presented are an advance toward the realization of shape-controlled multimetallic nanoparticles tailored to each potential application.     

Head–Tail Asymmetry as the Determining Factor in the Formation of Polymer Cubosomes or Hexasomes in a Rod–Coil Amphiphilic Block Copolymer

The self‐assembly of a rod–coil amphiphilic block copolymer (ABCP) led to Im m and Pn m polymer cubosomes and p6mm polymer hexasomes. This is the first time that these structures are observed in a rod–coil system. By varying the hydrophobic chain length, the initial concentration of the polymer solution, or the solubility parameter of the mixed solvent, head–tail asymmetry is adjusted to control the formation of polymer cubosomes or hexasomes. The formation mechanism of the polymer cubosomes was also studied. This research opens up a new way for further study of the bicontinuous and inverse phases in different ABCP systems.     

Coupling molecular rigidity and flexibility on fused backbones for NIR-II photothermal conversion

Great attention is being increasingly paid to photothermal conversion in the near-infrared (NIR)-II window (1000–1350 nm), where deeper tissue penetration is favored. To date, only a limited number of organic photothermal polymers and relevant theory have been exploited to direct the molecular design of polymers with highly efficient photothermal conversion, specifically in the NIR-II window. This work proposes a fused backbone structure locked via an intramolecular hydrogen bonding interaction and double bond, which favors molecular planarity and rigidity in the ground state and molecular flexibility in the excited state. Following this proposal, a particular class of NIR-II photothermal polymers are prepared. Their remarkable photothermal conversion efficiency is in good agreement with our strategy of coupling polymeric rigidity and flexibility, which accounts for the improved light absorption on going from the ground state to the excited state and nonradiative emission on going from the excited state to the ground state. It is envisioned that such a concept of coupling polymeric rigidity and flexibility will offer great inspiration for developing NIR-II photothermal polymers with the use of other chromophores.

Low bandgap and large deformation generally conflict each other. This work couples molecular rigidity and flexibility by intramolecular hydrogen bonds and double bonds to achieve NIR-II light absorption and reinforced internal conversion at the same time.     

The core of a chain complete poset with no one-way infinite fence and no tower

Like dismantling for finite posets, a perfect sequence = P : of a chain complete posetP represents a canonical procedure to produce a coreP . It has been proved that if the posetP contains no infinite antichain then this coreP is a retract ofP andP has the fixed point property iffP has this property. In this paper the condition of having no infinite antichain is replaced by a weaker one. We show that the same conclusion holds under the assumption thatP does not contain a one-way infinite fence or a tower.Supported by a grant from The National Natural Science Foundation of China.