Single‐electron transfer‐living radical polymerization of oligo(ethylene oxide) methyl ether methacrylate in the absence and presence of air

The efficient Cu(0) wire‐catalyzed single‐electron transfer‐living radical polymerization (SET‐LRP) of oligo(ethylene oxide) methyl ether methacrylate (OEOMA) in DMSO and binary mixtures of DMSO with H₂O is reported. Addition of 10–80% H₂O to DMSO resulted in an increase in the apparent rate constant of propagation ( ), corresponding to an increase in the polarity and extent of disproportionation. At higher H₂O content, decreases, and in H₂O is slightly lower than that in DMSO. This unexpected behavior was attributed to the physical inaccessibility of Cu(0) wire catalyst to the hydrophobic reactive centers of OEOMA and initiator which self‐assemble in H₂O into micellar aggregates and vesicles. This hypothesis was confirmed by the faster polymerization in H₂O than in DMSO during catalysis with Cu(0) nanoparticles generated by disproportionation of CuBr. SET‐LRP of OEOMA can be performed in protic and dipolar aprotic solvents in air by the addition of hydrazine hydrate. The polymerization exhibited no induction period and identical as in the degassed experiment, and led to polymers with narrow molecular weigh distribution. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3110–3122     

Gadolinium(III)‐Hydroxy Ladders Trapped in Succinate Frameworks with Optimized Magnetocaloric Effect

Two kinds of inorganic gadolinium(III)‐hydroxy “ladders”, [2×n] and [3×n], were successfully trapped in succinate (suc) coordination polymers, [Gd₂(OH)₂(suc)₂(H₂O)]_n ? 2n H₂O ( 1 ) and [Gd₆(OH)₈(suc)₅(H₂O)₂]_n ? 4n H₂O ( 2 ), respectively. Such coordination polymers could be regarded as alternating inorganic–organic hybrid materials with relatively high density. Magnetic and heat capacity studies reveal a large cryogenic magnetocaloric effect (MCE) in both compounds, namely (ΔH=70 kG) 42.8 J kg^?1 K^?1 for complex 1 and 48.0 J kg^?1 K^?1 for complex 2 . The effect of the high density is evident, which gives very large volumetric MCEs up to 120 and 144 mJ cm^?3 K^?1 for complexes 1 and 2 , respectively.     

Simulation of nuclide migration in a middle- and low-level radioactive waste repository based on GMS

Journal of Radioanalytical and Nuclear Chemistry - Groundwater is the most important factor contributing to the diffusion and migration of radionuclides in the repository. In this paper, the...     

Reversible Photoinduced Conversion of Unprecedented Norbornadiene-Based Photoswitches with Redox-Active Naphthalene Diimide Functionalities

An unprecedented compound class of functional organic hybrids consisting of a photoswitchable norbornadiene building block and a redoxactive chromophore, namely naphthalene diimide, were designed and synthesized. Within these structures the capability of rylene chromophores to function as a redox active catalyst upon their photoexcitation was utilized to initiate the oxidative back-conversion of the in situ formed quadricyclane unit to its norbornadiene analogue. In this way successive photoexcitation at two different wavelengths enabled a controlled photoswitching between the two isomerical states of the hybrids. Beyond this prove of concept, the dependency of the reaction rate to the intramolecular distance of the two functional molecular building blocks as well as the concentration of the photoexcited sample was monitored. The experimental findings and interpretations were furthermore supported by quantum chemical investigations.     

Structure and electrochemical performance of LiFePO4 cathode materials modified with carbon coating and metal doping

Journal of Solid State Electrochemistry - LiFePO4 cathode material is considered as a competitive material for lithium-ion battery, but its poor electronic and ionic conductivity hinder its further...     

Enhanced Crystal Quality of Perovskite via Protonated Graphitic Carbon Nitride Added in Carbon-Based Perovskite Solar Cells

The quality of perovskite layers has a great impact on the performance of perovskite solar cells (PSCs). However, defects and related trap sites are generated inevitably in the solution-processed polycrystalline perovskite films. It is meaningful to reduce and passivate the defect states by incorporating additive into the perovskite layer to improve perovskite crystallization. Here an environmental friendly 2D nanomaterial protonated graphitic carbon nitride (p-g-C\begin{document}$_3$\end{document}N\begin{document}$_4$\end{document}) was successfully synthesized and doped into perovskite layer of carbon-based PSCs. The addition of p-g-C\begin{document}$_3$\end{document}N\begin{document}$_4$\end{document} into perovskite precursor solution not only adjusts nucleation and growth rate of methylammonium lead tri-iodide (MAPbI\begin{document}$_3$\end{document}) crystal for obtaining flat perovskite surface with larger grain size, but also reduces intrinsic defects of perovskite layer. It is found that the p-g-C\begin{document}$_3$\end{document}N\begin{document}$_4$\end{document} locates at the perovskite core, and the active groups -NH\begin{document}$_2$\end{document}/NH\begin{document}$_3$\end{document} and NH have a hydrogen bond strengthening, which effectively passivates electron traps and enhances the crystal quality of perovskite. As a result, a higher power conversion efficiency of 6.61% is achieved, compared with that doped with g-C\begin{document}$_3$\end{document}N\begin{document}$_4$\end{document} (5.93%) and undoped one (4.48%). This work demonstrates a simple method to modify the perovskite film by doping new modified additives and develops a low-cost preparation for carbon-based PSCs.     

From borophosphate to fluoroborophosphate: a rational design of fluorine-induced birefringence enhancement

The introduction of oxofluoride anion into anionic group assists to tune optical properties owing to the change of coordination,electronegativity,and according anionic framework.Here,we proposed a rational design of new compounds by fluorine-driven structure and optical property evolution.A new borophosphate Ba_2BP_3O_(11)with the monoclinic space group P2_1/c has been synthesized in the sealed system.Ba_2BP_3O_(11)exhibits a rare P–O–P bridge formation,which is the first example in alkaline-earth metal borophosphates.By further substituting[BO_4]~(3-)with[BO_3F]~(4-),the first alkaline-earth metal/lead fluoroborophosphates M_2BP_2O_8F (M=Ba and Pb) with the same space group were designed.Since the scissors effect of fluorine,in M_2BP_2O_8F (M=Ba and Pb),a BO_3F tetrahedron corner-sharing with three PO_4tetrahedra forms 1D chains along the b-axial direction,which are filled by MO_n(M=Ba/Pb,n=5,6,8) distorted polyhedra.The first principles calculation shows that the borophosphate Ba_2BP_3O_(11)has a birefringence about 0.013@1,064 nm,while the fluoroborophosphates M_2BP_2O_8F (M=Ba and Pb) have the values of 0.035 and 0.043@1,064 nm,respectively.Such an apparent enhancement in birefringence is derived from synergies of the oxyfluoride and cation.The introduction of fluorine-containing heteroanionic groups provides a feasible strategy to design novel promising optical materials.     

Ultrahigh-intensity optical slow-wave structure

We report the development of corrugated "slow-wave" plasma guiding structures with application to quasiphase-matched direct laser acceleration of charged particles and generation of a wide spectrum of electromagnetic radiation. These structures support guided propagation at intensities up to 2 x 10(17) W/cm(2), limited by our current laser energy and side leakage. Hydrogen and argon plasma waveguides up to 1.5 cm in length with corrugation period as short as 35 microm are generated in a cryogenic cluster jet. Experimental data are consistent with simulations showing periodic modulations of the laser pulse intensity.     

Synergic Enhancement of High-density Polyethylene through Ultrahigh Molecular Weight Polyethylene and Multi-flow Vibration Injection Molding: A Facile Fabrication with Potential Industrial Prospects

General-purpose plastics with high strength and toughness have been in great demand for structural engineering applications. To achieve the reinforcement and broaden the application scope of high-density polyethylene(HDPE), multi-flow vibration injection molding(MFVIM) and ultrahigh molecular weight polyethylene(UHMWPE) are synergistically employed in this work. Herein, the MFVIM has better shear layer control ability and higher fabrication advantage for complex parts than other analogous novel injection molding technologies reported.The reinforcing effect of various filling times and UHMWPE contents as well as the corresponding microstructure evolution are investigated.When 5 wt% UHMWPE is added, MFVIM process with six flow times thickens the shear layer to the whole thickness. The tensile strength and modulus increase to 2.14 and 1.39 times, respectively, compared to neat HDPE on the premise of remaining 70% impact strength. Structural characterizations indicate that the enhancement is attributed to the improvement of shish-kebab content and lamellae compactness, as well as related to the corresponding size distributions of undissolved UHMWPE particles. This novel injection molding technology with great industrial prospects provides a facile and effective strategy to broaden the engineering applications of HDPE materials. Besides, excessive UHMWPE may impair the synergistic enhancement effect, which is also reasonably explained.