Boosting the reversibility of Zn anodes via synergistic cation-anion interface adsorption with addition of multifunctional potassium polyacrylate.

Rechargeable aqueous Zn batteries have the edge in resource reserve, cost, energy and conversion efficiency due to the inherent features of metal Zn anodes. However, the application of Zn-based batteries is being seriously hindered by Zn dendrites and water-induced side-reactions. Here, potassium polyacrylate (K-PAM) is proposed as the electrolyte additive to form a synergistic cation-anion interface on Zn surface. The carboxyl anions and K+ cations are preferentially adsorbed on the Zn surface due to the intrinsic surfactant characteristics, which could homogenize Zn plating and suppress parasitic reactions. The synergistic regulation of K-PAM additive endows the ZnZn symmetric cells with excellent cyclic durability of 1250 h at 1 mA cm-2, which is significantly better than the polyacrylic acid additive only with carboxyl anions. Moreover, trace K-PAM addition into traditional ZnSO4 electrolyte endows the ZnCu batteries with a considerable average Coulombic efficiency of 99.2 %. Additionally, higher capacity retention and excellent cycling stability of ZnVO2 cells further mark K-PAM as a potentially impressive aqueous electrolyte additive for high-performance Zn-based batteries. This work will provide a promising method for the synergistic regulation with cations and anions of electrolyte additives to improve the stability and reversibility of Zn anodes.

Synthesis and Electrochemical Properties of Aluminum Hexafluorophosphate.

We report the first synthesis of aluminum hexafluorophosphate (Al(PF6)3) and its electrochemical properties in dimethyl sulfoxide (DMSO). The single crystal structure of the synthesized Al(PF6)3 is revealed as [Al(DMSO)6](PF6)3, and 0.25 M Al(PF6)3 in DMSO with high ionic conductivity is obtained. The purity of this electrolyte was further confirmed with nuclear magnetic resonance spectroscopy and electrospray ionization mass spectrometry. We then demonstrated the reversibility of Al deposition-stripping in this electrolyte using scanning electron microscopy and an X-ray photoelectron spectroscopy depth profiling study. The parasitic reaction involving DMSO decomposition during Al deposition is also identified via gas chromatography/electron ionization mass spectrometry.

Arctigenin inhibits human breast cancer cell proliferation, migratory and invasive abilities and epithelial to mesenchymal transition by targeting 4EBP1.

Breast cancer (BC) is one of the most common types of cancer with the highest morbidity rate amongst all cancers in women worldwide. Arctigenin is isolated from the seeds of Asteraceae lappa and exhibits anti-inflammatory and anti-viral effects. The present study aimed to investigate the effect of arctigenin on BC cells and to explore the regulation of arctigenin on eukaryotic translation initiation factor 4E binding protein 1 (4EBP1) expression. To do so, MDA-MB-231 and BT549 cells were treated with arctigenin at various concentrations (0, 5, 10, 20 and 40 µM). Cells treated with 40 µM arctigenin were transfected with pcDNA3.1-4EBP1 or NC control. Cell Counting Kit-8 assay was used to determine cell proliferation, reverse transcription quantitative PCR was used to evaluate the transfection efficiency, western blotting was used to detect relative protein expression and Transwell assays were performed to evaluate the migratory and invasive abilities of BC cells. The results demonstrated that arctigenin could inhibit the proliferation, migratory and invasive abilities, and epithelial to mesenchymal transition (EMT) of MDA-MB-231 and BT549 cells. Furthermore, arctigenin downregulated the expression of 4EBP1 in MDA-MB-231 and BT549 cells, whereas 4EBP1 overexpression could reverse the inhibiting effect of arctigenin on proliferation, migratory and invasive abilities, and EMT in MDA-MB-231 and BT549 cells. The findings suggested that arctigenin may inhibit human BC cell proliferation, migratory and invasive abilities, and EMT by targeting 4EBP1.

Synthesis of Heterocyclic Core-Expanded Bis-Naphthalene Tetracarboxylic Diimides.

A highly reactive bis-naphthalene tetracarboxylic diimide (bis-NDI) intermediate, TBrDNDI, was designed and synthesized for core-expanded NDIs. Based on this intermediate, we achieved 9- and 11-membered core-expanded bis-NDI derivatives. Through expanding the NDI core and introducing electron-donor or electron-acceptor groups, the frontier energy orbitals, optical and electrical properties of these bis-NDIs can be finely tuned to obtain air-stable ambipolar or n-type materials.

Remarkable enhancement of charge carrier mobility of conjugated polymer field-effect transistors upon incorporating an ionic additive.

Organic semiconductors with high charge carrier mobilities are crucial for flexible electronic applications. Apart from designing new conjugated frameworks, different strategies have been explored to increase charge carrier mobilities. We report a new and simple approach to enhancing the charge carrier mobility of DPP-thieno[3,2-b]thiophene-conjugated polymer by incorporating an ionic additive, tetramethylammonium iodide, without extra treatments into the polymer. The resulting thin films exhibit a very high hole mobility, which is higher by a factor of 24 than that of thin films without the ionic additive under the same conditions. On the basis of spectroscopic grazing incidence wide-angle x-ray scattering and atomic force microscopy studies as well as theoretical calculations, the remarkable enhancement of charge mobility upon addition of tetramethylammonium iodide is attributed primarily to an inhibition of the torsion of the alkyl side chains by the presence of the ionic species, facilitating a more ordered lamellar packing of the alkyl side chains and interchain π-π interactions.

[Effect of Zishen Huoxue Recipe on Pathomorphology in Coronary Heart Disease Rats with Shen Deficiency Blood Stasis Syndrome].

OBJECTIVE: To observe the effect of Zishen Huoxue Recipe (ZHR) on pathomorphology in coronary heart disease (CHD) rats with Shen deficiency blood stasis syndrome (SDBSS). METHODS: Totally 60 healthy Wistar rats were divided into the blank control group, the model group, high, middle, and low dose ZHR groups according to random digit table, 12 in each group. Myocardial ischemia SDBSS rat model was prepared by ligating the left anterior descending coronary artery and injecting hydrocortisone. ZHR physic liquor was administered to rats in high, middle, and low dose ZHR groups at the daily dose of 21.6, 10.8, 5.4 g/kg by gastrogavage for 7 successive days, equal volume of pure water was administered to rats in the blank control group and the model group by gastrogavage for 7 successive days. Rat heart was collected for pathomorphological observation under light microscope. RESULTS: In the model group the heart muscle fiber was swollen and deformed with widened space, loose and dropsy tissues. Blood vessels in myocardial mesenchymal were dilated, infiltrated with more inflammatory cells. Myocardial cells were markedly swollen, degenerated, or necrotic, with caryolysis or disappearance of partial nuclear. A large amount of collagen fibrous tissue became hyperplasia. Endocardial blood vessels were swollen and degenerated with infiltration of few inflammatory cells. Epicardium tissue and structure were destroyed and got hyperplasia. Swollen, degenerated, or necrotic vessels could be seen, with infiltration of more inflammatory cells and collagen deposition. Pathomorphological injuries were alleviated in each ZHR group. The higher ZHR concentration, the milder the injury degree of myocardial tissue, the more limited range of damage. CONCLUSION: ZHR could attenuate pathomorphological injuries of myocardial ischemia rats with SDBSS and regulate myocardial function, thus improving myocardial ischemia in CHD rats with SDBSS.

Highly Sensitive Thin-Film Field-Effect Transistor Sensor for Ammonia with the DPP-Bithiophene Conjugated Polymer Entailing Thermally Cleavable tert-Butoxy Groups in the Side Chains.

The sensing and detection of ammonia have received increasing attention in recent years because of the growing emphasis on environmental and health issues. In this paper, we report a thin-film field-effect transistor (FET)-based sensor for ammonia and other amines with remarkable high sensitivity and satisfactory selectivity by employing the DPP-bithiophene conjugated polymer pDPPBu-BT in which tert-butoxycarboxyl groups are incorporated in the side chains. This polymer thin film shows p-type semiconducting property. On the basis of TGA and FT-IR analysis, tert-butoxycarboxyl groups can be transformed into the -COOH ones by eliminating gaseous isobutylene after thermal annealing of pDPPBu-BT thin film at 240 °C. The FET with the thermally treated thin film of pDPPBu-BT displays remarkably sensitive and selective response toward ammonia and volatile amines. This can be attributed to the fact that the elimination of gaseous isobutylene accompanies the formation of nanopores with the thin film, which will facilitate the diffusion and interaction of ammonia and other amines with the semiconducting layer, leading to high sensitivity and fast response for this FET sensor. This FET sensor can detect ammonia down to 10 ppb and the interferences from other volatile analytes except amines can be negligible.

Significant Improvement of Semiconducting Performance of the Diketopyrrolopyrrole-Quaterthiophene Conjugated Polymer through Side-Chain Engineering via Hydrogen-Bonding.

Three diketopyrrolopyrrole (DPP)-quaterthiophene conjugated polymers, pDPP4T-1, pDPP4T-2, and pDPP4T-3, in which the molar ratios of the urea-containing alkyl chains vs branching alkyl chains are 1:30, 1:20, and 1:10, respectively, were prepared and investigated. In comparison with pDPP4T without urea groups in the alkyl side chains and pDPP4T-A, pDPP4T-B, and pDPP4T-C containing both linear and branched alkyl chains, thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3 exhibit higher hole mobilities; thin-film mobility increases in the order pDPP4T-1 < pDPP4T-2 < pDPP4T-3, and hole mobility of a thin film of pDPP4T-3 can reach 13.1 cm(2) V(-1) s(-1) after thermal annealing at just 100 °C. The incorporation of urea groups in the alkyl side chains also has an interesting effect on the photovoltaic performances of DPP-quaterthiophene conjugated polymers after blending with PC71BM. Blended thin films of pDPP4T-1:PC71BM, pDPP4T-2:PC71BM, and pDPP4T-3:PC71BM exhibit higher power conversion efficiencies (PCEs) than pDPP4T:PC71BM, pDPP4T-A:PC71BM, pDPP4T-B:PC71BM, and pDPP4T-C:PC71BM. The PCE of pDPP4T-1:PC71BM reaches 6.8%. Thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3 and corresponding thin films with PC71BM were characterized with AFM, GIXRD, and STEM. The results reveal that the lamellar packing order of the alkyl chains is obviously enhanced for thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3; after thermal annealing, slight inter-chain π-π stacking emerges for pDPP4T-2 and pDPP4T-3. Blends of pDPP4T-1, pDPP4T-2, and pDPP4T-3 with PC71BM show a more pronounced micro-phase separation. These observations suggest that the presence of urea groups may further facilitate the assemblies of these conjugated polymers into nanofibers and ordered aggregation of PC71BM.

New conjugated molecules with two and three dithienyldiketopyrrolopyrrole (DPP) moieties substituted at meta positions of benzene toward p- and n-type organic photovoltaic materials.

Two conjugated molecules, TADPP3 and TADPP2-TT, are reported, in which three and two dithienyldiketopyrrolopyrrole (DPP) moieties, respectively, are substituted at the meta positions of benzene. Based on cyclic voltammetry and absorption data, TADPP3 and TADPP2-TT possess similar HOMO and LUMO energies of about -5.2 and -3.4 eV, respectively. Thin films of TADPP3 and TADPP2-TT exhibit p-type semiconducting behavior with hole mobilities of 2.36×10(-3) and 3.76×10(-4)  cm(2) V(-1) s(-1) after thermal annealing. Molecules TADPP3 and TADPP2-TT were utilized as p-type photovoltaic materials to fabricate organic solar cells after blending with phenyl C71 butyric acid methyl ester (PC71BM) and phenyl C61 butyric acid methyl ester (PC61BM). The relatively low JSC and fill factor values can be attributed to poor film morphologies based on AFM and XRD studies. A solar cell with a thin film of TADPP3 with PC71BM in a weight ratio of 1:2 exhibits a high open-circuit voltage (VOC) of 0.99 V and a power conversion efficiency (PCE) of 2.47 %. Interestingly, TADPP3 can also be employed as an n-type photovoltaic material. The blended thin film of TADPP3 with P3HT in a weight ratio of 1:2 gave a high VOC of 1.11 V and a PCE of 1.08 % after thermal annealing.

New organic semiconductors with imide/amide-containing molecular systems.

Due to their high electron affinities, chemical and thermal stabilities, π-conjugated molecules with imide/amide frameworks have received considerable attentions as promising candidates for high-performance optoelectronic materials, particularly for organic semiconductors with high carrier mobilities. The purpose of this Research News is to give an overview of recent advances in development of high performance imide/amide based organic semiconductors for field-effect transistors. It covers naphthalene diimide-, perylene diimide- and amide-based conjugated molecules and polymers for organic semiconductors.

Extended conjugated donor-acceptor molecules with E-(1,2-difluorovinyl) and diketopyrrolopyrrole (DPP) moieties toward high-performance ambipolar organic semiconductors.

Two diketopyrrolopyrrole (DPP)-based donor-acceptor (D-A) conjugated molecules, DPP-F and DPP-2F, which contain E-(1,2-difluorovinyl) moieties, are reported. The LUMO energies of DPP-F and DPP-2F were estimated to be -3.49 and -3.70 eV, respectively, based on their redox potentials and absorption spectral data; these values were clearly lowered because of the incorporation of electron-withdrawing E-(1,2-difluorovinyl) moieties. Organic field-effect transistors (OFETs) with thin films of DPP-F and DPP-2F were successfully fabricated with conventional techniques. Based on the respective transfer and output characteristics measured in an inert atmosphere, thin films of DPP-2F display ambipolar semiconducting behavior with hole and electron mobilities reaching 0.42 and 0.80 cm(2) V(-1) s(-1), respectively. The as-prepared OFET of DPP-2F already shows high hole and electron mobilities that are not influenced remarkably by thermal annealing. For thin films of DPP-F, only p-type semiconducting behavior was observed in both an inert atmosphere and air, and the hole mobility increased to 0.1 cm(2) V(-1) s(-1) after thermal annealing. XRD and AFM studies were performed with thin films of DPP-F and DPP-2F after annealing at different temperatures.

Thiepin-fused heteroacenes: simple synthesis, unusual structure, and semiconductors with less anisotropic behavior.

The simple one-pot syntheses of sulfur-rich thiepin-fused heteroacences with an alkylidene-fluorene framework, THA1 and THA6 (thiepin-fused heteroacene 1 or 6, in which the thiepin is conjugated at both ortho positions with SCH3 or SC6 H13 , respectively), is reported. Based on electrochemical studies and theoretical calculations, their LUMO energies are relatively low (-3.26 eV), and their HOMO and HOMO-1 orbitals are nearly degenerate. The thiepin ring contributes mainly to HOMO-1 and LUMO orbitals, however, HOMO orbitals dominantly reside on thienoacence rings. Within the crystal of THA1, the molecules adopt a herringbone arrangement and multiple intermolecular interactions lead to the formation of a 2D network. Interestingly, THA6 shows totally different intermolecular arrangements. Organic field-effect transistor (OFET) devices show both compounds exhibiting p-type semiconducting behavior. Thin films or microcrystals of THA1 possess relatively high hole mobility. Moreover, the mobilities of the microcrystal of THA1 along three directions are in the same order, thus the hole-carrier transporting within the hexagonal-plane of microcrystal of THA1 exhibits less anisotropic behavior. In comparison, both thin films and microrods of THA6 show low hole mobilities. This agrees well with the intermolecular arrangements and interactions within crystal of THA6. Further theoretical calculations reveal that significant intermolecular electronic coupling among HOMO-1 orbitals and sulfur atoms play an important role in intermolecular electronic coupling for THA1.