Flexible hybrid photodetector based on silver sulfide nanoparticles and multi-walled carbon nanotubes.

Herein, we reported a wearable photodetector based on hybrid nanocomposites, such as carbon materials and biocompatible semiconductor nanocrystals (NCs), exhibiting excellent photoresponsivity and superior durability. Currently, semiconductor nanocrystal quantum dots (QDs) containing heavy metals, such as lead or cadmium (in the form of lead sulfide (PbS) and cadmium sulfide (CdS)), are known to display excellent detection properties and are thus widely employed in the fabrication of photodetectors. However, the toxic properties of these heavy metals are well known. Hence, in spite of their enormous potential, the QDs based on these heavy metals are not generally preferred in biological or biomedical applications. These limitations, though, can be overcome by the judicious choice of alternate materials such as silver sulfide (Ag2S) NCs, which are biocompatible and exhibit multiple excitons in Ag2S QDs. The other chosen component is a carbon-based material, such as the multi-walled carbon nanotube (MWCNT), which is preferred primarily due to its strong and superior mechanical durability. In this study, a hybrid nanocomposite film was synthesized from Ag2S NCs and MWCNTs by a simple one-step fabrication process using ultrasonic irradiation. Additionally, this method did not involve any chemical functionalization or post-processing step. The size of Ag2S NCs in the hybrid film was controlled by the irradiation time and the power of the ultrasonic radiation. Further, appropriate composition ratio of the hybrid composite was optimized to balance the photo-response and mechanical durability of the photodetector. Thus, using this synthetic method, an excellent photoresponsivity property of the device was demonstrated for a near-infrared (NIR) light source with various light wavelengths. Furthermore, no visible change in photoresponsivity was observed for bending motions up to 105 cycles and for a range of angles (0-60°). This novel method provides an eco-friendly alternative to existing functional composites containing toxic heavy metals and is a promising approach for the development of wearable optoelectronic devices.

Near-infrared-emitting nanoparticles activate collagen synthesis via TGFß signaling.

Research efforts towards developing near-infrared (NIR) therapeutics to activate the proliferation of human keratinocytes and collagen synthesis in the skin microenvironment have been minimal, and the subject has not been fully explored. Herein, we describe the novel synthesis Ag2S nanoparticles (NPs) by using a sonochemical method and reveal the effects of NIR irradiation on the enhancement of the production of collagen through NIR-emitting Ag2S NPs. We also synthesized Li-doped Ag2S NPs that exhibited significantly increased emission intensity because of their enhanced absorption ability in the UV-NIR region. Both Ag2S and Li-doped Ag2S NPs activated the proliferation of HaCaT (human keratinocyte) and HDF (human dermal fibroblast) cells with no effect on cell morphology. While Ag2S NPs upregulated TIMP1 by only twofold in HaCaT cells and TGF-ß1 by only fourfold in HDF cells, Li-doped Ag2S NPs upregulated TGF-ß1 by tenfold, TIMP1 by 26-fold, and COL1A1 by 18-fold in HaCaT cells and upregulated TGF-ß1 by fivefold and COL1A1 by fourfold in HDF cells. Furthermore, Ag2S NPs activated TGF-ß1 signaling by increasing the phosphorylation of Smad2 and Smad3. The degree of activation was notably higher in cells treated with Li-doped Ag2S NPs, mainly caused by the higher PL intensity from Li-doped Ag2S NPs. Ag2S NPs NIR activates cell proliferation and collagen synthesis in skin keratinocytes and HDF cells, which can be applied to clinical light therapy and the development of anti-wrinkle agents for cosmetics.

Multilayer fabrication of unobtrusive poly(dimethylsiloxane) nanobrush for tunable cell adhesion.

Precise modulation of polymer brush in its thickness and grafting density can cause unexpected cell behaviors and regulated bioactivities. Herein, a nanoscale poly(dimethylsiloxane) (PDMS) brush was employed to use as a controllable material for cell adhesion. Facile fabrication of ultrathin monolayer PDMS nanobrush on an underlying substrate facilitated regaining cell adhesion through long-range cell attractive forces such as the van der Waals forces. We showed that cell adhesion is diminished by increasing the number of nanobrush layers, causing a gradual decrease of the effectiveness of the long-range force. The result demonstrates that ultrathin PDMS nanobrush can either promote or inhibit cell adhesion, which is required for various biomedical fields such as tissue-engineering, anti-fouling coating, and implantable biomaterials and sensors.

Synthesis of silver sulfide nanoparticles and their photodetector applications.

Silver sulfide nanoparticles (Ag2S NPs) are currently being explored as infrared active nanomaterials that can provide environmentally stable alternatives to heavy metals such as lead. In this paper, we describe the novel synthesis of Ag2S NPs by using a sonochemistry method and the fabrication of photodetector devices through the integration of Ag2S NPs atop a graphene sheet. We have also synthesized Li-doped Ag2S NPs that exhibited a significantly enhanced photodetector sensitivity via their enhanced absorption ability in the UV-NIR region. First-principles calculations based on a density functional theory formalism indicated that Li-doping produced a dramatic enhancement of NIR photoluminescence of the Ag2S NPs. Finally, high-performance photodetectors based on CVD graphene and Ag2S NPs were demonstrated and investigated; the hybrid photodetectors based on Ag2S NPs and Li-doped Ag2S NPs exhibited a photoresponse of 2723.2 and 4146.0 A W-1 respectively under a light exposure of 0.89 mW cm-2 at 550 nm. Our novel approach represents a promising and effective method for the synthesis of eco-friendly semiconducting NPs for photoelectric devices.

Micropillar arrays as potential drug screens: Inhibition of micropillar-mediated activation of the FAK-Src-paxillin signaling pathway by the CK2 inhibitor CX-4945.

Here, we demonstrate the possible applications of micropillar arrays in screening anti-metastasis drugs. Human lung adenocarcinoma A549 cells incubated in multiwell plates containing micropillars exhibited markedly different physical/biochemical behavior depending on pillar dimensions. In particular, A549 cells grown in plates containing 2-µm diameter, 16-µm pitched pillar arrays showed epithelial-to-mesenchymal transition (EMT)-like behavior; cell body elongation, and highly increased activation of the focal adhesion kinase (FAK)-Src-paxillin signaling cascade. FAK is the most prominent kinase involved in dynamic regulation of the actin cytoskeleton and cell adhesion, migration, and invasion. Activation of FAK, a hallmark of cancer cell adhesion and migration, is normally induced by various growth factors, such as transforming growth factor-ß (TGF-ß). Here, we found that pillar-mediated activation of signaling molecules mimicked that induced by TGF-ß. Notably, micropillar arrays with specific dimensions accelerated the elongation of cells, an effect linked to the activation of signaling molecules related to EMT. Micropillar-induced FAK activation could be arrested by the casein kinase-2 (CK2) inhibitor CX-4945, a drug candidate with activity against TGF-ß-induced cancer cell metastasis, demonstrating the possibility of using inorganic microstructures for cell-based drug screening. STATEMENT OF SIGNIFICANCE: In this work, we have fabricated flexible substrates with regular arrays of micrometersized pillars, and used them to grow A549 human lung adenocarcinoma cells. Cells exhibit dramatically different behavior depending on the intervals of pillars. Especially, cells grown in certain pillar structures show epithelial-to mesenchmal transition (EMT)-like morphology and related molecules, which is similar to the activation obtained using expensive cytokine TGF-ß. Based on the fact that pillar arrays may activate EMT like transition, screening of anti-cancer drug using pillar arrays have demonstrated as well in our work. Our study confirms that mechanical stimulation may exert similar effects with chemical stimulation, and such mechanical structures could be used as a large-scale drug screening platforms. Cell morphogenesis on engineered substrate is not new, but the present work could be distinguished with its unique fabrication process that can mass produce the structures and it could be applied for high-throughput drug screening. Also, we suggest the formation of focal adhesions on pillar structures and consequent strain as the possible mechanism behind the observed EMT-like transition. Currently, we are working on full-scale profiling of metabolomics and proteomics of cells grown in large-scale pillar arrays as well.

Effects of substrate conductivity on cell morphogenesis and proliferation using tailored, atomic layer deposition-grown ZnO thin films.

We demonstrate that ZnO films grown by atomic layer deposition (ALD) can be employed as a substrate to explore the effects of electrical conductivity on cell adhesion, proliferation, and morphogenesis. ZnO substrates with precisely tunable electrical conductivity were fabricated on glass substrates using ALD deposition. The electrical conductivity of the film increased linearly with increasing duration of the ZnO deposition cycle (thickness), whereas other physical characteristics, such as surface energy and roughness, tended to saturate at a certain value. Differences in conductivity dramatically affected the behavior of SF295 glioblastoma cells grown on ZnO films, with high conductivity (thick) ZnO films causing growth arrest and producing SF295 cell morphologies distinct from those cultured on insulating substrates. Based on simple electrostatic calculations, we propose that cells grown on highly conductive substrates may strongly adhere to the substrate without focal-adhesion complex formation, owing to the enhanced electrostatic interaction between cells and the substrate. Thus, the inactivation of focal adhesions leads to cell proliferation arrest. Taken together, the work presented here confirms that substrates with high conductivity disturb the cell-substrate interaction, producing cascading effects on cellular morphogenesis and disrupting proliferation, and suggests that ALD-grown ZnO offers a single-variable method for uniquely tailoring conductivity.

Europium-doped gadolinium sulfide nanoparticles as a dual-mode imaging agent for T1-weighted MR and photoluminescence imaging.

We present a facile synthesis of europium-doped gadolinium sulfide (GdS:Eu(3+)) opto-magnetic nanoparticles (NPs) via sonochemistry. Their photoluminescence and strong paramagnetic properties enable these NPs to be utilized as an in vitro cell imaging and in vivo T(1)-weighted MR imaging probe. The GdS:Eu(3+) NPs have a prominent longitudinal (r(1)) relaxivity value, which is a critical parameter for T(1)-weighted MR imaging. Here, we showed not only their strong positive contrast effect to blood vessels and organs of mice, but also blood half-life and biodistribution including clearance from organs, in order to assess the GdS:Eu(3+) NPs as a competent nanocrystal-based T(1) contrast agent. We further showed confocal images of breast cancer cells containing GdS:Eu(3+) NPs to evaluate as a photoluminescence probe. Dual-mode imaging capability obtained from the GdS:Eu(3+) NPs will allow target-oriented cellular imaging as well as the resulting disease-specific MR imaging.

A facile reduction of Eu3+ to Eu2+ in gadolinium monosulfide nanoparticles using a mixed solvent of oleic acid/hexadecylamine.

We prepared GdS:Eu(3+) by simple thermal decomposition under 1-dodecanethiol. A reduction process was observed from Eu(3+) to Eu(2+) when oleic acid and hexadecylamine were injected into GdS:Eu(3+). Under UV excitation, GdS:Eu(3+) showed an intense orange-red emission and GdS:Eu(2+) showed a broad green band.

Synthesis of highly magnetic graphite-encapsulated FeCo nanoparticles using a hydrothermal process.

The graphite encapsulation of metal alloy magnetic nanoparticles has attracted attention for biological applications because of the high magnetization of the encapsulated particles. However, most of the synthetic methods have limitations in terms of scalability and economics because of the demanding synthetic conditions and low yields. Here, we show that well controlled graphite-encapsulated FeCo core-shell nanoparticles can be synthesized by a hydrothermal method, simply by mixing Fe/Co with sucrose as a carbon source. Various Fe/Co metal ratios were used to determine the compositional dependence of the saturation magnetization and relaxivity coefficient. Transmission electron microscopy indicated that the particle sizes were 7 nm. In order to test the capability of graphite-encapsulated FeCo nanoparticles as magnetic resonance imaging (MRI) contrast agents, these nanoparticles were solubilized in water by the nonspecific physical adsorption of sodium dodecylbenzene sulfonate.

Sonication treatment of CdTe/CdS semiconductor nanocrystals and their bio-application.

Ultrasonic irradiation of core/shell structures was shown to lead to low toxicity and high quantum yields relative to thermal methods for bio-application.