ON THE EXISTENCE WITH EXPONENTIAL DECAY AND THE BLOW-UP OF SOLUTIONS FOR COUPLED SYSTEMS OF SEMI-LINEAR CORNER-DEGENERATE PARABOLIC EQUATIONS WITH SINGULAR POTENTIALS

In this article,we study the initial boundary value problem of coupled semi-linear degenerate parabolic equations with a singular potential term on manifolds with corner singularities.Firstly,we introduce the corner type weighted p-Sobolev spaces and the weighted corner type Sobolev inequality,the Poincare′inequality,and the Hardy inequality.Then,by using the potential well method and the inequality mentioned above,we obtain an existence theorem of global solutions with exponential decay and show the blow-up in finite time of solutions for both cases with low initial energy and critical initial energy.Significantly,the relation between the above two phenomena is derived as a sharp condition.Moreover,we show that the global existence also holds for the case of a potential well family.     

Hyphenone A,the first 3,3-diisoprenylated bicyclic polyprenylated acylphloroglucinols as Cav3.1 T-type calcium channel inhibitor from Hypericum henryi

Hyphenone A (1), a new type of bicyclic polyprenylated acylphloroglucinols (BPAPs) featured with an unprecedented 3,3-diisoprenylated 1,3,5-trione core, were characterized from the roots of Hypericum henryi together with two new congeners (hyphenones B–C, 2–3) and five known biosynthetic related PPAPs. Biogenetically, 1 should be derived from a novel 3,3,5,5-tetraisoprenylated MPAPs precursor. Their structures were elucidated by comprehensive spectroscopic data and X-ray diffraction. Moreover, 1–3 were identified as the first PPAPs type Ca_v3.1 T-type calcium channel (TTCC) inhibitors, with IC₅₀ values of 7.07, 6.19, and 5.47 μM, respectively.     

Bifunctional Phosphine Ligand Enabled Gold‐Catalyzed Alkynamide Cycloisomerization: Access to Electron‐Rich 2‐Aminofurans and Their Diels–Alder Adducts

By using biphenyl‐2‐ylphosphines functionalized with a remote tertiary amino group as a ligand, readily available acetylenic amides are directly converted into 2‐aminofurans devoid of any electron‐withdrawing and hence deactivating/stabilizing substituents. These highly electron‐rich furans have rarely been prepared, let alone applied in synthesis, because of their high reactivities and low stabilities associated with the electron‐rich nature of the furan ring. In this work, these reactive furans smoothly undergo either in situ intermolecular Diels–Alder reactions to deliver highly functionalized/substituted aniline products or intramolecular ones to furnish carbazole‐4‐carboxylates in mostly good to excellent yields. This work offers general and expedient access to this class of little studies electron‐rich furans and should lead to exciting opportunities for their applications.     

Autonomous conveyer gel driven by frontal polymerization

Autonomous mechanical mass transportation for cargos on the microscale with no need of continuous external powering is of great scientific and technological interest due to their extensive applications. However, it is still challenging to create a self‐driven system applicable to diverse micromaterial transportation demands. In this work, we developed a novel autonomous conveyer gel driven by frontal polymerization (FP). The chemical wave produced in FP was stable, and self‐propagating with a constant velocity, which can be easily monitored by thermal imaging or fluorescence labeling. We investigated the influence of the initiation temperature, swelling ratio of the gel substrate, and the size of the cargos on the motion of driven behavior. Results showed that the driving velocity can be well controlled by altering the initiation temperatures of FP. The swelling ratio and the size of the cargos had a key impact on the feasibility of self‐driven behavior. In addition, powerful driven capability by FP was demonstrated by successfully transporting cargos in series, and further applied for targeted synthesis of CdS nanocrystals. The methodology developed here provides an effective way to convert chemical energy to mechanical work, and may be useful in energy conversion and utilization, mass transportation and other applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1323‐1331     

Mono‐ and Dinuclear Phosphorescent Rhenium(I) Complexes: Impact of Subcellular Localization on Anticancer Mechanisms

Elucidation of relationship among chemical structure, cellular uptake, localization, and biological activity of anticancer metal complexes is important for the understanding of their mechanisms of action. Organometallic rhenium(I) tricarbonyl compounds have emerged as potential multifunctional anticancer drug candidates that can integrate therapeutic and imaging capabilities in a single molecule. Herein, two mononuclear phosphorescent rhenium(I) complexes ( Re1 and Re2 ), along with their corresponding dinuclear complexes ( Re3 and Re4 ), were designed and synthesized as potent anticancer agents. The subcellular accumulation of Re1–Re4 was conveniently analyzed by confocal microscopy in situ in live cells by utilizing their intrinsic phosphorescence. We found that increased lipophilicity of the bidentate ligands could enhance their cellular uptake, leading to improved anticancer efficacy. The dinuclear complexes were more potent than the mononuclear counterparts. The molecular anticancer mechanisms of action evoked by Re3 and Re4 were explored in detail. Re3 with a lower lipophilicity localizes to lysosomes and induces caspase‐independent apoptosis, whereas Re4 with higher lipophilicity specially accumulates in mitochondria and induces caspase‐independent paraptosis in cancer cells. Our study demonstrates that subcellular localization is crucial for the anticancer mechanisms of these phosphorescent rhenium(I) complexes.     

Efficiency Improvement in Polymer Light‐Emitting Diodes by “Far‐Field” Effect of Gold Nanoparticles

The “far‐field” effect of metal nanoparticles (NPs), when chromophores localized nearby metal NPs (typically the distance >λ/10), is an important optical effect to enhance emission in photoluminescence. The far‐field effect originates mainly from the interaction between origin emission and mirror‐reflected emission, resulting in the increased irradiative rate of chromophores on the mirror‐type substrate. Here, the far‐field effect is used to improve emission efficiency of polymer light‐emitting diodes (PLEDs). A universal performance improvement is achieved for the full visible light (red, green, blue) PLEDs, utilizing gold (Au) NPs to modify the indium tin oxide (ITO) substrates; this is shown by experimental and theoretical simulation to mainly come from the far‐field effect. The optimized distance, between the NPs and chromophores with visible light emission ranging from 400 to 700 nm, is 80–120 nm. Thus the scope of the far‐field may overlap the light‐emitting profile very well to enhance the efficiency of optoelectronic devices. The 30–40% enhancement is obtained for different color‐emitting materials through distance optimization. The far‐field effect is demonstrated to enhance device performance for materials in the full‐visible spectral range, which extends the optoelectric applications of Au NPs.     

Characteristics of Friedel pairs and diffraction contrast tomography with non‐perpendicular rotation axis

The characteristics of Friedel pairs in diffraction contrast tomography (DCT) are studied in the condition that the rotation axis of the sample is not exactly perpendicular to the incident X‐ray direction. For the rotation axis approximately aligned along the vertical direction, the Friedel pairs close to the horizontal plane are insensitive to the non‐perpendicularity of the rotation axis, and can be used to refine the sample‐to‐detector distance and X‐ray energy, while the Friedel pairs close to the vertical direction are sensitive to the non‐perpendicularity of the rotation axis, and can be used to determine the rotation axis orientation. The correct matching proportion of Friedel pairs decreases with increasing non‐perpendicularity of the rotation axis. A method of data processing considering rotation axis misalignment is proposed, which significantly increases the correct matching and indexing proportions of the diffraction spots. A pure aluminium polycrystalline sample is investigated using DCT at beamline 4W1A of Beijing Synchrotron Radiation Facility. Based on the analysis of Friedel pairs, the sample‐to‐detector distance and X‐ray energy are refined to be 8.67 mm and 20.04 keV, respectively. The non‐perpendicular angle of the rotation axis is calculated to be 0.10°. With these refined geometric parameters, the matching proportion of the spatial position of diffraction spots is 90.62%. Three‐dimensional reconstruction of the sample with 13 grains is realised using the algebraic reconstruction technique. It is demonstrated that the precise correction of the orientation of the sample rotation axis is effective in DCT suffering from rotation axis misalignment, and the higher accuracy in determining the rotation axis is expected to improve the reconstruction precision of grains.     

Quantitative 31P‐NMR spectroscopy for the determination of fosfomycin and impurity A in pharmaceutical products of fosfomycin sodium or calcium

A quantitative ³¹P‐NMR method for the determination of fosfomycin and impurity A in pharmaceutical products of fosfomycin sodium or calcium has been developed. In this method, coaxial inserts containing trimethyl phosphate are used as external standard. The method is convenient and robust, and gives both high accuracy and precision. It is shown that an accurate determination is possible using different probes and coaxial inserts. Copyright © 2015 John Wiley & Sons, Ltd.