Atomic-Scale Dispersed Fe-Based Catalysts Confined on Nitrogen-Doped Graphene for Li-S Batteries: Polysulfides with Enhanced Conversion Efficiency

Lithium-sulfur batteries have been considered as potential electrochemical energy-storage devices owing to their satisfactory theoretical energy density. Nonetheless, the inferior conversion efficiency of polysulfides in essence leads to fast capacity decay during the discharge/charge cycle. In this work, it is successfully demonstrated that the conversion efficiency of lithium polysulfides is remarkably enhanced by employing a well-distributed atomic-scale Fe-based catalyst immobilized on nitrogen-doped graphene (Fe@NG) as a coating of separator in lithium-sulfur batteries. The quantitative electrocatalytic efficiency of the conversion of lithium polysulfides is determined through cyclic voltammetry. It is also proven that the Fe-N_X configuration with highly catalytic activity is quite beneficial for the conversion of lithium polysulfides. In addition, the adsorption and permeation experiments distinctly indicate that the strong anchoring effect, originated from the charge redistribution of N doping into the graphene matrix, inhibits the movement of lithium polysulfides. Thanks to these advantages, if the as-prepared Fe@NG catalyst is combined with polypropylene and applied as a separator (Fe@NG/PP) in Li-S batteries, a high initial capacity (1616 mA h g⁻¹ at 0.1 C), excellent capacity retention (93 % at 0.2 C, 70 % at 2 C), and superb rate performance (820 mA h g⁻¹ at 2 C) are achieved.     

Undersampled Windowed Exponentials and Their Applications

We characterize the completeness and frame/basis property of a union of under-sampled windowed exponentials of the form

$$ {\mathcal{F}}(g): =\bigl\{ e^{2\pi i n x}: n\ge 0\bigr\} \cup \bigl\{ g(x)e^{2\pi i nx}: n< 0\bigr\} $$

for \(L^{2}[-1/2,1/2]\) by the spectra of the Toeplitz operators with the symbol \(g\). Using this characterization, we classify all real-valued functions \(g\) such that \({\mathcal{F}}(g)\) is complete or forms a frame/basis. Conversely, we use the classical non-harmonic Fourier series theory to determine all \(\xi \) such that the Toeplitz operators with the symbol \(e^{2\pi i \xi x}\) is injective or invertible. These results demonstrate an elegant interaction between frame theory of windowed exponentials and Toeplitz operators. Finally, we use our results to answer some open questions in dynamical sampling, and derivative samplings on Paley-Wiener spaces of bandlimited functions.

     

Monodisperse Six-Armed Starbursts based on Truxene-Cored Multibranched Oligofluorenes: Design,Synthesis, and Stabilized Lasing Characteristics

A series of monodisperse six-armed conjugated starbursts ( Tr1F , Tr2F , and Tr3F ) containing a truxene core and multibranched oligofluorene bridges capped with diphenylamine (DPA) units has been designed, synthesized, and investigated as robust gain media for organic semiconductor lasers (OSLs). The influence of electron-rich DPA end groups on their optoelectronic characteristics has been discussed at length. DPA cappers effectively raise HOMO levels of the starbursts, thus enhancing the hole injection and transport ability. Solution-processed electroluminescence devices based on the resulting six-armed starbursts exhibited efficient deep-blue electroluminescence with clear reduced turn-on voltages (3.2–3.5 V). Moreover, the resulting six-armed molecules showed stabilized electroluminescence and amplified spontaneous emission with low thresholds (27.4–63.9 nJ pulse⁻¹), high net gain coefficients (80.1–101.3 cm⁻¹), and small optical loss (2.6–4.4 cm⁻¹). Distributed feedback OSLs made from Tr3F exhibited a low lasing threshold of 0.31 kW cm⁻² (at 465 nm). The results suggest that the construction of truxene-centered six-armed conjugated starbursts with the incorporation of DPA units can effectively enhance EL properties by precisely regulating the HOMO energy levels, and further optimizing their optical gain properties.     

Assembly-enhanced triplet-triplet annihilation upconversion in the aggregation formed by Schiff-base Pt(Ⅱ) complex grafting-permethyl-β-CD and 9,10-diphenylanthracence dimer

Water-soluble triplet sensitizer with permethyl-β-cyclodextrin(PMCD) grafting on a Schiff-base Pt(Ⅱ)complex(Pt-2),in which PMCD unit serves as a host for binding the acceptors and the Schiff-base Pt(Ⅱ)complex serves as a triplet sensitizer,was synthesized to investigate the effect of supramolecular complexation and assembly on the triplet-triplet annihilation upconversion emission in water.9,10-Diphenylanthracence(DPA) carboxylate(A-1) and its dimer(A-2) in which two DPA carboxylate were covalently linked with an alkyl chain were synthesized as triplet acceptors which also play a role of guest molecules for PMCD.A-1 and A-2 showed high affinity with PMCD,and A-2 can readily aggregate in water and form micron sized assemblies due to the hydrophobic effect and π-π stacking of anthracene core in A-2.The efficiency of TTA-UC was demonstrated to be enhanced by a synergistic effect of host-guest complexation of Pt-2 with A-2 and the self-aggregation of the acceptor A-2,which facilitated the energy transfer and energy fusion among donor and acceptor.     

Peroxidase-Like Platinum Clusters Synthesized by Ganoderma lucidum Polysaccharide for Sensitively Colorimetric Detection of Dopamine

The sensitive and selective detection of dopamine (DA) is very important for the early diagnosis of DA-related diseases. In this study, we reported the colorimetric detection of DA using Ganoderma lucidum polysaccharide (GLP) stabilized platinum nanoclusters (Pt_n-GLP NCs). When Pt₆₀₀-GLP NCs was added, 3,3’,5,5’-tetramethylbenzidine (TMB) was rapidly catalyzed and oxidized to blue oxTMB, indicating the peroxidase-like activity of Pt₆₀₀-GLP NCs. The catalytic reaction on the substrate TMB followed the Michaelis-Menton kinetics with the ping-pong mechanism. The mechanism of the colorimetric reaction was mainly due to the formation of hydroxyl radical (•OH). Furthermore, the catalytic reaction of Pt₆₀₀-GLP NCs was used in the colorimetric detection of DA. The linear range for DA was 1–100 μM and the detection limit was 0.66 μM. The sensitive detection of DA using Pt-GLP NCs with peroxidase-like activity offers a simple and practical method that may have great potential applications in the biotechnology field.     

Generating Function of the Tilings of an Aztec Rectangle with Holes

We consider a generating function of the domino tilings of an Aztec rectangle with several unit squares removed from the boundary. Our generating function involves two statistics: the rank of the tiling and half number of vertical dominoes as in the Aztec diamond theorem by Elkies, Kuperberg, Larsen and Propp. In addition, our work deduces a combinatorial explanation for an interesting connection between the number of lozenge tilings of a semihexagon and the number of domino tilings of an Aztec rectangle.     

Air‐Stable Spirofluorene‐Containing Ladder‐Type Bis(alkynyl)borane Compounds with Readily Tunable Full Color Emission Properties

A series of air‐stable spiro‐fused ladder‐type boron(III) compounds has been designed, synthesized, and the electrochemistry and photophysical behavior have been characterized. By simply varying the substituents on the pyridine ring and extending the π‐conjugation of the spiro framework, the emission color of these compounds can be easily fine‐tuned spanning the visible spectrum from blue to red. All compounds exhibit a broad and structureless emission band across the entire visible region, assigned as an intramolecular charge‐transfer transition originating from the thiophene of the spiro framework to the pyridine‐borane moieties. In addition, these compounds demonstrate high photoluminescence quantum yields of up to 0.81 in dichloromethane solution and 0.86 in doped thin films. Some of the compounds have also been employed as emissive materials, in which solution‐processed organic light‐emitting devices (OLEDs) with tunable emission colors spanning the visible spectrum from blue, green to red have been realized, demonstrating the potential applications of these boron compounds in OLEDs.     

Phase separation dynamics of a poly(vinyl methyl ether)/polystyrene (PVME/PS) blend studied by ultrafast differential scanning calorimetry

In this work, ultrafast differential scanning calorimetry (UFDSC) is used to study the dynamics of phase separation. Taking poly(vinyl methyl ether)/polystyrene (PVME/PS) blend as the example, we firstly obtained the phase diagram that has lower critical solution temperature (LCST), together with the glass transition temperature (T_g) of the homogeneous blend with different composition. Then, the dynamics of the phase separation of the PVME/PS blend with a mass ratio of 7:3 was studied in the time range from milliseconds to hours, by the virtue of small time and spatial resolution that UFDSC offers. The time dependence of the glass transition temperature (T_g) of PVME‐rich phase, shows a distinct change when the annealing temperature (T_a) changes from below to above 385 K. This corresponds to the transition from the nucleation and growth (NG) mechanism to the spinodal decomposition (SD) mechanism, as was verified by morphological and rheometric investigations. For the SD mechanism, the temperature‐dependent composition evolution in PVME‐rich domain was found to follow the Williams–Landel–Ferry (WLF) laws. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1357–1364     

Triphenylamine derivatized phenylacetylene macrocycle with large two-photon absorption cross-section

A phenylacetylene macrocycle (PAM) derivative containing triphenylamine as the framework was synthesized in one-step Sonogashira coupling. The photophysical and electrochemical properties were investigated in details. This hexamer shows significant enhancement in two-photon absorption cross-section relative to reported PAM derivatives.