Impact of Mesoporous Silicon Template Pore Dimension and Surface Chemistry on Methylammonium Lead Trihalide Perovskite Photophysics

© 2020 Wiley-VCH GmbH In influencing fundamental properties—and ultimately device performance—of lead halide perovskites, interfacial interactions play a major role, notably with regard to carrier diffusion and recombination. Here anodized porous Si (pSi) as well as porous silica particles are employed as templates for formation of methylammonium lead trihalide nanostructures. This allows synthesis of relatively small perovskite domains and comparison of associated interfacial chemistry between as-prepared hydrophobic hydrideterminated functionalities and hydrophilic oxide-terminated surfaces. While physical confinement of MAPbBr3 has a uniform effect on carrier lifetime, pore size (7–18 nm) of the silicon-containing template has a sensitive influence on perovskite photoluminescence (PL) wavelength maximum. Furthermore, identity of the surface functionality of the template significantly alters the PL quantum efficiency, with lowest PL intensity associated with the H-terminated pSi and the most intense PL affiliated with the oxideterminated pSi surface. These effects are explored for green-emitting MAPbBr3 as well as infrared-emitting MAPbI3. In addition, the role of silicon surface chemistry on the time-dependent stability of these perovskites packaged within a given mesoporous template is also evaluated, specifically, a lack of miscibility between MAPbI3 and the H-terminated pSi template results in a diffusion of this specific perovskite composition eluting from this porous matrix over time

Investigation of a Mesoporous Silicon Based Ferromagnetic Nanocomposite

A semiconductor/metal nanocomposite is composed of a porosified silicon wafer and embedded ferromagnetic nanostructures. The obtained hybrid system possesses the electronic properties of silicon together with the magnetic properties of the incorporated ferromagnetic metal. On the one hand, a transition metal is electrochemically deposited from a metal salt solution into the nanostructured silicon skeleton, on the other hand magnetic particles of a few nanometres in size, fabricated in solution, are incorporated by immersion. The electrochemically deposited nanostructures can be tuned in size, shape and their spatial distribution by the process parameters, and thus specimens with desired ferromagnetic properties can be fabricated. Using magnetite nanoparticles for infiltration into porous silicon is of interest not only because of the magnetic properties of the composite material due to the possible modification of the ferromagnetic/superparamagnetic transition but also because of the biocompatibility of the system caused by the low toxicity of both materials. Thus, it is a promising candidate for biomedical applications as drug delivery or biomedical targeting

Critical Role of PI3K/Akt/GSK3β in Motoneuron Specification from Human Neural Stem Cells in Response to FGF2 and EGF

Fibroblast growth factor (FGF) and epidermal growth factor (EGF) are critical for the development of the nervous system. We previously discovered that FGF2 and EGF had opposite effects on motor neuron differentiation from human fetal neural stem cells (hNSCs), but the underlying mechanisms remain unclear. Here, we show that FGF2 and EGF differentially affect the temporal patterns of Akt and glycogen synthase kinase 3 beta (GSK3β) activation. High levels of phosphatidylinositol 3-kinase (PI3K)/Akt activation accompanied with GSK3β inactivation result in reduction of the motor neuron transcription factor HB9. Inhibition of PI3K/Akt by chemical inhibitors or RNA interference or overexpression of a constitutively active form of GSK3β enhances HB9 expression. Consequently, PI3K inhibition increases hNSCs differentiation into HB9+/microtubule-associated protein 2 (MAP2)+ motor neurons in vitro. More importantly, blocking PI3K not only enhances motor neuron differentiation from hNSCs grafted into the ventral horn of adult rat spinal cords, but also permits ectopic generation of motor neurons in the dorsal horn by overriding environmental influences. Our data suggest that FGF2 and EGF affect the motor neuron fate decision in hNSCs differently through a fine tuning of the PI3K/AKT/GSK3β pathway, and that manipulation of this pathway can enhance motor neuron generation

Suppression of Radiation-Induced Salivary Gland Dysfunction by IGF-1

Radiation is a primary or secondary therapeutic modality for treatment of head and neck cancer. A common side effect of irradiation to the neck and neck region is xerostomia caused by salivary gland dysfunction. Approximately 40,000 new cases of xerostomia result from radiation treatment in the United States each year. The ensuing salivary gland hypofunction results in significant morbidity and diminishes the effectiveness of anti-cancer therapies as well as the quality of life for these patients. Previous studies in a rat model have shown no correlation between induction of apoptosis in the salivary gland and either the immediate or chronic decrease in salivary function following gamma-radiation treatment.A significant level of apoptosis can be detected in the salivary glands of FVB mice following gamma-radiation treatment of the head and neck and this apoptosis is suppressed in transgenic mice expressing an activated mutant of Akt (myr-Akt1). Importantly, this suppression of apoptosis in myr-Akt1 mice preserves salivary function, as measured by saliva output, three and thirty days after gamma-radiation treatment. In order to translate these studies into a preclinal model we found that intravenous injection of IGF1 stimulated activation of endogenous Akt in the salivary glands in vivo. A single injection of IGF1 prior to exposure to gamma-radiation diminishes salivary acinar cell apoptosis and completely preserves salivary gland function three and thirty days following irradiation.These studies suggest that apoptosis of salivary acinar cells underlies salivary gland hypofunction occurring secondary to radiation of the head and neck region. Targeted delivery of IGF1 to the salivary gland of patients receiving head and neck irradiation may be useful in reducing or eliminating xerostomia and restoring quality of life to these patients

Distinct Patterns of DNA Damage Response and Apoptosis Correlate with Jak/Stat and PI3Kinase Response Profiles in Human Acute Myelogenous Leukemia

BACKGROUND:Single cell network profiling (SCNP) utilizing flow cytometry measures alterations in intracellular signaling responses. Here SCNP was used to characterize Acute Myeloid Leukemia (AML) disease subtypes based on survival, DNA damage response and apoptosis pathways. METHODOLOGY AND PRINCIPAL FINDINGS:Thirty four diagnostic non-M3 AML samples from patients with known clinical outcome were treated with a panel of myeloid growth factors and cytokines, as well as with apoptosis-inducing agents. Analysis of induced Jak/Stat and PI3K pathway responses in blasts from individual patient samples identified subgroups with distinct signaling profiles that were not seen in the absence of a modulator. In vitro exposure of patient samples to etoposide, a DNA damaging agent, revealed three distinct "DNA damage response (DDR)/apoptosis" profiles: 1) AML blasts with a defective DDR and failure to undergo apoptosis; 2) AML blasts with proficient DDR and failure to undergo apoptosis; 3) AML blasts with proficiency in both DDR and apoptosis pathways. Notably, AML samples from clinical responders fell within the "DDR/apoptosis" proficient profile and, as well, had low PI3K and Jak/Stat signaling responses. In contrast, samples from clinical non responders had variable signaling profiles often with in vitro apoptotic failure and elevated PI3K pathway activity. Individual patient samples often harbored multiple, distinct, leukemia-associated cell populations identifiable by their surface marker expression, functional performance of signaling pathway in the face of cytokine or growth factor stimulation, as well as their response to apoptosis-inducing agents. CONCLUSIONS AND SIGNIFICANCE:Characterizing and tracking changes in intracellular pathway profiles in cell subpopulations both at baseline and under therapeutic pressure will likely have important clinical applications, potentially informing the selection of beneficial targeted agents, used either alone or in combination with chemotherapy

In vitro dissolution behavior of hydrogenated amorphous silicon thin-film transistors

AbstractRecent developments in biodegradable nanostructured crystalline silicon and flexible silicon-based electronic devices raise the significant question of the stability of standard amorphous silicon transistor platforms in biologically relevant environments. In this work, we evaluate the biodegradation of hydrogenated amorphous silicon thin film transistors. Specifically, using a combination of gravimetric analysis, optical imaging, and X-ray fluorescence, we investigate the fundamental stability of a simple hydrogenated amorphous silicon thin film transistor structure immersed in phosphate-buffered saline at physiological temperature (37 °C). In addition to the possible galvanic influence of associated metal electrodes in the degradation of such devices, implications for future device platforms are also discussed.</jats:p

Template Pore Size and A-Site Cation Management Dictate Luminescence Efficiency, Stability, and Wavelength in Confined Perovskite Nanostructures

A-site cation composition is a useful lever in optimizing the photophysical properties and stability of metal halide perovskites (MHPs). Independent of this, straightforward preparative routes to MHP nanostructures that employ a single solid-state template with modest thermal requirements are also in demand. Here we employ both strategies in the fabrication and evaluation of luminescence properties of mixed formamidinium / cesium (CsxFA1-xPbBr3) and methylammonium / cesium (CsxMA1-xPbBr3) nanostructures formed within confining mesoporous silica of 4 nm and 7 nm average pore diameter. Use of such small pore oxide- terminated templates produce perovskite nanostructures in the strongly confined regime, with broadly tunable emission from green to sky blue (g). It is found that the smallest nanostructures that are formamidinium-rich exhibit the largest photoluminescence quantum efficiency values, but such values diminish by more than 50% in a 10-day period. In contrast, the same nanostructures formed within a 7 nm porous template retain their efficiency values over the same time window. The likely origins of this size-dependent behavior are discussed in terms of pore size-dependent capillary forces. Such routes may ultimately lead to improved light emitting diode designs composed of controlled quantum-confined perovskites of greater intrinsic stability than other emitters such as ligand-based colloidal nanocrystals

Synthesis of silicon nanocrystals with erbium-rich surface layers

A route to silicon nanocrystals with erbium-rich surface layers is described involving the initial pyrolysis of disilane to produce nucleation and growth of the Si core followed by a second thermal annealing step in the presence of the volatile complex Er(tmhd)(3) (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionato). These nanoparticles were structurally characterized by transmission electron microscopy, selected area electron diffraction, energy-dispersive X-ray analysis, and extended X-ray absorption fine structure methods, while spectroscopic characterization was achieved via photoluminescence and UV-visible absorption spectroscopies. The effects of altering the length of the pyrolysis oven and its temperature, the disilane flow rate, and the Er(tmhd)(3)/helium carrier gas flow rate on the mean nanoparticle feature size are noted. Interestingly, the characteristic 120 near-infrared photoluminescence at 1540 nm is not detected in the as-formed nanoparticles but can be observed after a brief vacuum anneal at 800 degreesC.1738338

UV ACTIVATION OF RECEPTOR TYROSINE KINASE-ACTIVITY

The exposure of mammalian cells to ultraviolet radiation (UV) may lead to DNA damage resulting in mutation and thus possibly cancer, while irradiation can further act as a potent tumour promoter. In addition UV induces p21ras-mediated signalling leading to activation of transcription factors such as AP-1 and NF-kappa B, as well as activation of the Src tyrosine kinase. This 'UV-response' has been well studied in mammalian cells and furthermore is conserved in yeast, however the most upstream components of this signal transduction pathway have remained elusive. Here we show that UV rapidly activates both the EGF receptor and insulin receptor, as shown by tyrosine phosphorylation of these receptors. We demonstrate that this activation is due to autophosphorylation as it only occurs in cells containing receptors with a functional kinase domain. We have further analysed the propagation of the UV-induced signal to downstream events such as, IRS-1 and Shc tyrosine phosphorylation, phosphatidylinositol 3-kinase activation, leukotriene synthesis, MAP kinase activation and gene induction all of which are activated by UV irradiation. Importantly, we demonstrate that in cells expressing a 'kinase-dead' receptor mutant the UV-response is inhibited, blocking leukotriene synthesis, MAP kinase activation and transcriptional induction. Furthermore, prior-stimulation of cells with UV appears to reduce further responsiveness to addition of growth factor suggesting a common signaling pathway. These data demonstrate a critical role for receptor-mediated events in regulating the response of mammalian cells to UV exposure

Rare earth doped silicon nanocrystals derived from an erbium amidinate precursor

We describe the use of Er(tBuNC(CH3)NtBu)(3) as a dopant source in the preparation of silicon nanocrystals, particularly as regards their observed structure, composition, and photophysical properties. These nanocrystals were prepared by the co-pyrolysis of Er(tBuNC(CH3)NtBu)(3) and disilane in a dilute helium stream at 1000 degreesC. Characterization methods include high resolution electron microscopy, selected area electron diffraction, energy dispersive x-ray measurements, extended x-ray absorption spectroscopy, and photoluminescence spectroscopy. In conditions identical to those used previously for beta-diketonate precursors, nanocrystals doped using this amidinate source are larger in size, of a narrower size distribution, and contain more erbium in the nanocrystal on average. Steady state photoluminescence measurements as a function of excitation wavelength confirm that the characteristic 1540 nm emission detected in these nanocrystals emit by a silicon exciton-mediated pathway. These results are a clear example of precursor dopant chemistry exerting a significant effect on resultant nanoparticle properties.15564364