Encapsulation of cationic iridium(iii) tetrazole complexes into a silica matrix: Synthesis, characterization and optical properties

Herein we report the easy incorporation of brightly phosphorescent cationic iridium(iii) tetrazole complexes into a silica based matrix via an easily scalable colloidal process. For this purpose, two cationic Ir(iii) emitters bearing 5-aryl tetrazole ligands (R-CN4) were selected: blue [F2IrPTZ-Me]+(C^N = F2ppy; N^N = PTZ-Me-2-(2-methyl-2H-tetrazol-5-yl)pyridine) and red [IrQTZ-Me]+(C^N = ppy; N^N = QTZ-Me-2-(2-methyl-2H-tetrazol-5-yl)quinoline). The cationic complexes were readily adsorbed to negatively charged silica nanoparticles and trapped in the sol-gel matrix. The sol-to-solid phase transfer was performed by using an innovative spray-freeze-drying technique, leading to the formation of phosphorescent solid micro-granules. The structural and optical characterisation of the Ir(iii) complexes together with SiO2nanoparticles, nanosols (Ir@SiO2) and powders (Ir@SiO2powders), revealed how the presence of the Ir(iii)-based complexes did not alter the morphology of the colloidal silica or granulated phases. Moreover, the silica matrix did not interfere with the optical properties of the embedded complexes. The distribution of [F2IrPTZ-Me]+and [IrQTZ-Me]+in the spray-freeze-dried powders was qualitatively evaluated by fluorescence microscopy, revealing how the luminescent particles were homogeneously dispersed all over the silica matrix. Interestingly, in aqueous solution the release of complex [F2IrPTZ-Me]+from the corresponding Ir@SiO2powder is almost negligible, therefore suggesting that a strong interaction occurs between the host-silica matrix and the Ir(iii) guest complex

The impact of stress on tumor growth: peripheral CRF mediates tumor-promoting effects of stress

<p>Abstract</p> <p>Introduction</p> <p>Stress has been shown to be a tumor promoting factor. Both clinical and laboratory studies have shown that chronic stress is associated with tumor growth in several types of cancer. Corticotropin Releasing Factor (CRF) is the major hypothalamic mediator of stress, but is also expressed in peripheral tissues. Earlier studies have shown that peripheral CRF affects breast cancer cell proliferation and motility. The aim of the present study was to assess the significance of peripheral CRF on tumor growth as a mediator of the response to stress in vivo.</p> <p>Methods</p> <p>For this purpose we used the 4T1 breast cancer cell line in cell culture and in vivo. Cells were treated with CRF in culture and gene specific arrays were performed to identify genes directly affected by CRF and involved in breast cancer cell growth. To assess the impact of peripheral CRF as a stress mediator in tumor growth, Balb/c mice were orthotopically injected with 4T1 cells in the mammary fat pad to induce breast tumors. Mice were subjected to repetitive immobilization stress as a model of chronic stress. To inhibit the action of CRF, the CRF antagonist antalarmin was injected intraperitoneally. Breast tissue samples were histologically analyzed and assessed for neoangiogenesis.</p> <p>Results</p> <p>Array analysis revealed among other genes that CRF induced the expression of SMAD2 and β-catenin, genes involved in breast cancer cell proliferation and cytoskeletal changes associated with metastasis. Cell transfection and luciferase assays confirmed the role of CRF in WNT- β-catenin signaling. CRF induced 4T1 cell proliferation and augmented the TGF-β action on proliferation confirming its impact on TGFβ/SMAD2 signaling. In addition, CRF promoted actin reorganization and cell migration, suggesting a direct tumor-promoting action. Chronic stress augmented tumor growth in 4T1 breast tumor bearing mice and peripheral administration of the CRF antagonist antalarmin suppressed this effect. Moreover, antalarmin suppressed neoangiogenesis in 4T1 tumors in vivo.</p> <p>Conclusion</p> <p>This is the first report demonstrating that peripheral CRF, at least in part, mediates the tumor-promoting effects of stress and implicates CRF in SMAD2 and β-catenin expression.</p

An assessment of sputtered nitrogen-doped nickel oxide for all-oxide transparent optoelectronic applications: The case of hybrid NiO:N/TiO2 heterostructure

ransition metal oxides present a unique category of materials due to their versatile optical, electrical and mechanical properties. Nickel oxide (NiO) is an intrinsic p-type oxide semiconductor. P-NiO with controllable and reproducible physico-chemical properties, if combined with transparency and low temperature (low-T) fabrication processes, can be fully exploited in many transparent and/or flexible devices for applications, like energy management (production, manipulation, storage), sensing, wearable and health care electronics, etc. Reproducibility, transparency and low-T fabrication processes of p-type NiO are the motivation of this work. Nitrogen is one of the dopants used for modifying the properties of NiO. Until now, nitrogen-doped NiO, has shown inferior properties than those of pure NiO. In this work, we present nitrogen-doped NiO (NiO:N) thin films with enhanced properties compared to those of the undoped NiO. The NiO:N films were grown by sputtering on room-temperature substrates in plasma containing 50% Ar and 50% (O2+N2) gases. The undoped NiO film was oxygen-rich, single-phase cubic NiO, having transmittance less than 20%. Upon doping with nitrogen, the films became more transparent (around 65%), had a wide direct band gap (up to 3.67 eV) and showed clear evidence of indirect band gap, 2.50-2.72 eV, depending on %(O2-N2) in plasma. The changes in the properties of the films such as structural disorder, energy band gap, Urbach states and resistivity were correlated with the incorporation of nitrogen in their structure. The optimum NiO:N film was used to form a diode with spin-coated, mesoporous on top of a compact, TiO2 film. The hybrid NiO:N/TiO2 heterojunction was transparent showing good output characteristics, as deduced using both I-V and Cheung’s methods. The diode’s transparency and characteristics were further enhanced upon thermal treatment and this was attributed to improved NiO:N properties with annealing. Transparent NiO:N films can be realized for all-oxide flexible optoelectronic devices

Transparent all-oxide hybrid NiON/TiO2 heterostructure for optoelectronic applications

Nickel oxide (NiO) is a p-type oxide and nitrogen is one of the dopants used for modifying its properties. Until now, nitrogen-doped NiO has shown inferior optical and electrical properties than those of pure NiO. In this work, we present nitrogen-doped NiO (NiO:N) thin films with enhanced properties compared to those of the undoped NiO thin film. The NiO:N films were grown at room temperature by sputtering using a plasma containing 50% Ar and 50% (O2 + N2) gases. The undoped NiO film was oxygen-rich, single-phase cubic NiO, having a transmittance of less than 20%. Upon doping with nitrogen, the films became more transparent (around 65%), had a wide direct band gap (up to 3.67 eV) and showed clear evidence of indirect band gap, 2.50–2.72 eV, depending on %(O2-N2) in plasma. The changes in the properties of the films such as structural disorder, energy band gap, Urbach states and resistivity were correlated with the incorporation of nitrogen in their structure. The optimum NiO:N film was used to form a diode with spin-coated, mesoporous on top of a compact, TiO2 film. The hybrid NiO:N/TiO2 heterojunction was transparent showing good output characteristics, as deduced using both I-V and Cheung’s methods, which were further improved upon thermal treatment. Transparent NiO:N films can be realized for all-oxide flexible optoelectronic devices

Effect of Electrolyte Concentration on the Electrochemical Performance of Spray Deposited LiFePO₄

LiFePO4 is a common electrode cathode material that still needs some improvements regarding its electronic conductivity and the synthesis process in order to be easily scalable. In this work, a simple, multiple-pass deposition technique was utilized in which the spray-gun was moved across the substrate creating a “wet film”, in which—after thermal annealing at very mild temperatures (i.e., 65 °C)—a LiFePO4 cathode was formed on graphite. The growth of the LiFePO4 layer was confirmed via X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy. The layer was thick, consisting of agglomerated non-uniform flake-like particles with an average diameter of 1.5 to 3 μm. The cathode was tested in different LiOH concentrations of 0.5 M, 1 M, and 2 M, indicating an quasi-rectangular and nearly symmetric shape ascribed to non-faradaic charging processes, with the highest ion transfer for 2 M LiOH (i.e., 6.2 × 10−9 cm2/cm). Nevertheless, the 1 M aqueous LiOH electrolyte presented both satisfactory ion storage and stability. In particular, the diffusion coefficient was estimated to be 5.46 × 10−9 cm2/s, with 12 mAh/g and a 99% capacity retention rate after 100 cycles

The thermo-electric nature of the Debye temperature

The Debye temperature is typically associated with the heat capacity of a solid and the cut-off of the possible lattice vibrations, but not necessarily to the electric conductivity of the material. By investigating III-V and II-VI compound semiconductors, we reveal that the Debye temperature represents a thermo-electric material parameter, connecting the thermal and electronic properties of a solid via a distinct power law

Assembly of quantum dots on peptide nanostructures and their spectroscopic properties

We present a chemical process for the decoration of self-assembled two-dimensional peptide fibrils with two different sizes of CdSe@ZnS core–shell quantum dots (Qdots) capped with trioctylphosphine oxide molecules. The attachment of the semiconducting nanoparticles to the fibrils is directed via disulfide bond between the quantum dot and cysteine aminoacids that are deliberately impeded in the peptide structures. A significant red shift in the emission spectra of the quantum dots is observed and attributed to the synergistic interaction between adjacent nanoparticles arranged on peptide film templates extending over hundreds of nanometer

A novel process to realize 4H-SiC nanowire arrays

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