Proton Self-Doped Polyaniline with High Electrochemical Activity for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries are promising energy storage devices due to their low cost, good ionic conductivity, and high safety. Conductive polyaniline is a promising cathode because of its redox activity, but because the neutral electrolyte protonates only weakly, it displays limited electrochemical activity. A polyaniline cathode is developed with proton self-doping from manganese metal-organic frameworks (Mn-MOFs) that alleviates the deprotonation and electrochemical activity concerns arising during the charge/discharge process.

Hierarchical spheroidal MOF-derived MnO@C as cathode components for high-performance aqueous zinc ion batteries.

Aqueous zinc-ion batteries (AZIBs) have shown great potential as energy storage devices owing to their high energy density, low cost, and low toxicity. Typically, high performance AZIBs incorporate manganese-based cathode materials. Despite their advantages, these cathodes are limited by significant capacity fading and poor rate performance due to the dissolution and disproportionation of manganese.

Using a two-step method of surface mechanical attrition treatment and calcium ion implantation to promote the osteogenic activity of mesenchymal stem cells as well as biomineralization on a β-titanium surface.

Surface treatment is known as a very efficient measure by which to modulate the surface properties of biomaterials in terms of grain structure, topography, roughness and chemistry to determine the osseointegration of implants. In this work, a two-step method of surface modification was employed to impart high osteogenic activity and biomineralization capacity on a Ti-25Nb-3Mo-2Sn-3Zr alloy (a type of β-titanium named TLM). The preliminary surface mechanical attrition treatment (SMAT) refined the average grain size from 170 ± 19 μm to 74 ± 8 nm in the TLM surface layer and promoted the surface to be much rougher and more hydrophilic.

Regulating the Interlayer Spacing of Vanadium Oxide by In Situ Polyaniline Intercalation Enables an Improved Aqueous Zinc-Ion Storage Performance.

Vanadium pentoxide (VO) possesses great potential for application as cathode materials for aqueous zinc-ion batteries due to abundant valences of vanadium. Unfortunately, the inferior electronic conductivity and confined interlayer spacing of pristine VO are not able to support fast Zn diffusion kinetics, leading to significant capacity degradation, the dissolution of active species, and unsatisfactory cycling life. Herein, Zn (de)intercalation kinetics is improved by the design of in situ polyaniline (PANI)-intercalated VO.

Coordinately Unsaturated Manganese-Based Metal-Organic Frameworks as a High-Performance Cathode for Aqueous Zinc-Ion Batteries.

The slow Zn intercalation/deintercalation kinetics in cathodes severely limits the electrochemical performance of aqueous zinc-ion batteries (ZIBs). Herein, we demonstrate a new kind of coordinately unsaturated manganese-based metal-organic framework (MOF) as an advanced cathode for ZIBs. Coordination unsaturation of Mn is performed with oxygen atoms of two adjacent -COO.

Electrostatic Self-Assembly Synthesis of Three-Dimensional Mesoporous Lepidocrocite-Type Layered Sodium Titanate as a Superior Adsorbent for Selective Removal of Cationic Dyes via an Ion-Exchange Mechanism.

Three-dimensional mesoporous lepidocrocite-type layered sodium titanate (LST) was constructed at room temperature by the electrostatic interaction between TiO nanosheets and Na ions. The results of a systematic X-ray diffraction investigation manifested the transition from the TiO nanosheets phase to the titanate/titania phase, which determined a phase diagram as a function of the temperature and NaCl concentration. In addition, scanning electron microscopy, inductively coupled plasma-mass spectrometry, thermogravimetric and differential thermal, N adsorption-desorption, Raman spectroscopy, Fourier transform infrared spectroscopy, as well as ζ-potential analyses were utilized for adequate characterization of the LST physical and chemical properties.

Tailored Hydrothermal Synthesis of Specific Facet-Dominated TiO Nanocrystals from Lepidocrocite-Type Layered Titanate Nanosheets: Systematical Investigation and Enhanced Photocatalytic Performance.

A series of samples including leaf-like and rod-like rutile TiO nanoparticles with various facets exposed on the surface, parallelepiped-shaped anatase nanoparticles with [111] vertical facet exposed on the surface, irregular anatase nanoparticles, microsized six-point star-like anatase aggregates, and almond-like brookite aggregates had been hydrothermally synthesized from lepidocrocite-type layered titanate nanosheets. A systematical investigation was established to uncover the phase transition and morphological evolution from nanosheets to TiO polymorphs, and a phase diagram was determined by adjusting the synthesis parameters of the pH value and temperature. Two kinds of mechanisms composed of the dissolution-deposition process following Ostwald's ripening mechanism and the topochemical conversion process following Ostwald's step rule had been proposed based on the time-dependent hydrothermal experiments.

Identification of viral SIM-SUMO2-interaction inhibitors for treating primary effusion lymphoma.

Primary effusion lymphoma (PEL) is an aggressive B-cell malignancy without effective treatment, and caused by the infection of Kaposi's sarcoma-associated herpesvirus (KSHV), predominantly in its latent form. Previously we showed that the SUMO2-interacting motif within the viral latency-associated nuclear antigen (LANASIM) is essential for establishment and maintenance of KSHV latency. Here, we developed a luciferase based live-cell reporter system to screen inhibitors selectively targeting the interaction between LANASIM and SUMO2.

Selective Hydrogen Generation from Formic Acid with Well-Defined Complexes of Ruthenium and Phosphorus-Nitrogen PN(3) -Pincer Ligand.

An unsymmetrically protonated PN(3) -pincer complex in which ruthenium is coordinated by one nitrogen and two phosphorus atoms was employed for the selective generation of hydrogen from formic acid. Mechanistic studies suggest that the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved.

Ir(III)-catalyzed C-H alkynylation of arenes under chelation assistance.

An efficient and mild Ir(III)-catalyzed, chelation assisted C-H alkynylation of arenes has been developed using hypervalent iodine alkynes as alkynylating reagents. A broad scope of N-phenyl-2-aminopyridines and 2-phenoxypyridines has been established as effective substrates for this C-H functionalization and the desired alkynylated products were isolated in moderate to high yields.

Rhodium(iii)-catalyzed annulation of arenes with alkynes assisted by an internal oxidizing N-O bond.

Rh(iii)-catalyzed C-H activation of 3-aryl-dihydroisoxazoles in the coupling with diarylacetylenes has been developed under redox-neutral conditions. This reaction occurred under mild conditions with no by-product, and the N-O bond functions as an oxidizing directing group, leading to efficient synthesis of isoquinolines functionalized with a proximal secondary alcohol.

C-H and H-H bond activation via ligand dearomatization/rearomatization of a PN³P-rhodium(I) complex.

A neutral complex PN(3)P-Rh(I)Cl (2) was prepared from a reaction of the PN(3)P pincer ligand (1) with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene). Upon treatment with a suitable base, H-H and C(sp(2))-H activation reactions can be achieved through the deprotonation/reprotonation of one of the N-H arms and dearomatization/rearomatization of the central pyridine ring with the oxidation state of Rh remaining I.

Prediction of mechanical properties of multilayer gradient hydroxyapatite reinforced poly(vinyl alcohol) gel biomaterial.

Functional graded materials provided us one new concept for artificial articular cartilage design with graded component and graded structure. In this article, a novel functional material design was proposed by functionalizing hydroxyapatite (HA) particles in poly(vinyl alcohol) (PVA) hydrogel. The goal of the present study was to fabricate a multilayer gradient HA/PVA gel biocomposites through layer-by-layer casting method combining with freeze/thaw cycle technology and establish a mechanical model to predict the compressive mechanical properties of multilayer gradient gel biocomposites.

Cubic and doubly-fused cubic samarium clusters from Sm(II)-mediated reduction of organic azides and azobenzenes.

A polynuclear samarium imido complex [(L)Sm(4)(μ(3)-NSiMe(3))(4)] (2) featuring a cubane-like cluster has been synthesized from the reaction of an organic azide and a samarium(II) complex [(L)SmI(2)Li(2)(THF)(Et(2)O)(2)] (1). In addition, this divalent samarium starting material (1) reacts with azobenzene to give the first example of a well-defined doubly-fused cubic imido-cluster [(L)Sm(6)(μ(3)-NPh)(4)(μ(4)-NPh)(2)I(2)(THF)(2)] (4) in addition to a major cubic complex [(L)Sm(4)(μ(3)-NPh)(4)] (3).

A heterometallic sandwich complex of europium(II) for luminescent studies.

A divalent europium complex [(L(Ph))(2)Eu{K(THF)(2)}(2)] (L(Ph) = Ph(2)Si(NAr)(2), Ar = 2,6-(i)Pr(2)C(6)H(3)) (THF = Tetrahydrofuran) (2), which has a sandwich structure with potassium-arene π interactions, was synthesized in high yield via a one-pot process. This complex has been fully characterized, and luminescent studies showed that the 528 nm emission peak can be attributed to the 4f-5d transition of Eu(2+).

Rh(III)-catalyzed oxidative coupling of N-aryl-2-aminopyridine with alkynes and alkenes.

[RhCp*Cl(2)](2) (1-2 mol %) can catalyze the oxidative coupling of N-aryl-2-aminopyridines with alkynes and arylates to give N-(2-pyridyl)indoles and N-(2-pyridyl)quinolones, respectively, using Cu(OAc)(2) as an oxidant. Coupling with styrenes gave mono- and/or disubstituted olefination products.

Rh-catalyzed oxidative coupling between primary and secondary benzamides and alkynes: synthesis of polycyclic amides.

A methodology for the high yield and facile synthesis of isoquinolones from benzamides and alkynes via the oxidative ortho C-H activation of benzamides has been developed. Ag(2)CO(3) proved to be an optimal oxidant when MeCN was used as a solvent, and [RhCp*Cl(2)](2) was utilized as an efficient catalyst. Both N-alkyl and N-aryl secondary benzamides can be applied as effective substrates.

Tetracarboxylate-based Co(II), Ni(II) and Cu(II) three-dimensional coordination polymers: syntheses, structures and magnetic properties.

Methylenediisophthalic acid (H(4)MDIP), as semi-rigid 'V'-shaped carboxylate ligands, react with CoO, NiO and Cu(NO(3))(2)·3H(2)O to give three novel coordination polymers [H(3)O](2)[Co(3)(MDIP)(2)]·2DMF (1), [Ni(2)(HMDIP)(μ(2)-OH)(H(2)O)(3)(DMF)]·4H(2)O·DMF (2) and [Cu(3)(MDIP)(μ(2)-OH)(2)(H(2)O)(4)]·6.5H(2)O (3) (DMF = N,N'-dimethylformamide). All compounds have been characterized by thermogravimetric analysis, IR spectroscopy, elemental and single-crystal X-ray diffraction analyses.

Mn(II)-based MIL-53 analogues: synthesis using neutral bridging mu2-ligands and application in liquid-phase adsorption and separation of C6-C8 aromatics.

Four Mn(II)-based MIL-53 single crystals were prepared using four neutral pyridine N-oxides as bridging mu(2)-ligands. In the case of 4,4'-bipridine-N,N'-dioxide (BPNO), the infinite manganese oxide chains were further interconnected by BPNO besides BDC, which allows 1D channels to be accessible for guest molecules. The liquid-phase adsorption and separation of C6-C8 aromatics using the evacuated compound as an absorbent were investigated via crystal-to-crystal transformations.

Lanthanide-alkali metal sandwich complexes: synthesis, structure, and solvent-mediated redox transformations, and one-dimensional frameworks assembled through cation-arene pi interactions.

Reaction of the potassium salt of amido ligand [Ph(2)Si(NAr)(2)](2-) (L, Ar = 2,6-iPr(2)C(6)H(3)) and LnI(2)(thf)(2) (Ln = Sm, Yb) gives sandwich complexes [(L)(2)Ln{K(Et(2)O)}(2)] (Ln = Sm (2), Yb (3)) with potassium-arene pi interactions. Reaction of 2 with azobenzene gave the dimeric samarium cluster [(L)(2)Sm(2)(mu-eta(2):eta(2)-N(2)Ph(2))(2){K(thf)(2)}(2)] (4) and the tetrameric [(L)Sm(4) (mu-eta(2):eta(2)-N(2)Ph(2))(3) (mu(3)-NPh)(2)(thf)(3)] (5). On the other hand, the reaction of 2 with alpha-diimines ligands ArN=CRCR=NAr (DAD, R = H, Me) gives two Sm(III) complexes: polymeric [(L)Sm{(ArN)RC=CR(NAr)}K](n) (R = H (6), Me (7)) assembled through cation-pi interactions and byproduct [{(L)(2)Sm}{K(thf)(6)}] (8).

Stabilization of imidosamarium(III) cubane by amidinates.

An imidosamarium(III) cubane has been prepared from the reductive cleavage of azobenzene by a divalent samarium bis(amidinate) complex, indicating that the "spectrator" bis(amidinate) and the resulting imido ligands help to stabilize the cubane framework. The cubane-type imido cluster is a novel unit in lanthanide chemistry.