Intracellular delivery of top-down fabricated tunable nano-plasmonic resonators.

Engineered plasmonic structures fabricated using top-down technologies have demonstrated huge enhancements in the optical response of molecules, including Raman scattering. However, providing a sufficient number of such top-down fabricated nanostructures in solution has been a nontrivial task which has limited their potential in intracellular applications. Here we report the development of a protocol for the intracellular delivery of tunable nanoplasmonic resonators fabricated via scalable top-down techniques. This offers excellent possibilities towards the real-time parallel optical detection of intracellular molecular events.

Subcellular resolution mapping of endogenous cytokine secretion by nano-plasmonic-resonator sensor array.

Local extracellular signaling is central for cellular interactions and organizations. We report a novel sensing technique to interrogate extracellular signaling at the subcellular level. We developed an in situ immunoassay based on giant optical enhancement of a tunable nano-plasmonic-resonator array fabricated by nanoimprint lithography. Our nanoplasmonic device significantly increases the signal-to-noise ratio to enable the first time submicrometer resolution quantitative mapping of endogenous cytokine secretion. Our study shows a markedly high local interleukin-2 (IL-2) concentration within the immediate vicinity of the cell which finally validates a decades-old hypothesis on autocrine physiological concentration and spatial range. This general sensing technique can be applied for a broad range of cellular communication studies to improve our understanding of subcellular signaling and function.

Intense pulsed light induced platinum-gold alloy formation on carbon nanotubes for non-enzymatic glucose detection.

We demonstrated a novel method for the formation of alloy nano-islands on carbon nanotube (CNT). The two metal layers (Pt, Au) were sputtered on CNTs and the intense pulsed light (IPL) was irradiated on the metal layers. The absorbed light provides enough energy for the diffusion mixing between Pt and Au, forming Pt-Au alloy phase. While the alloy is being formed by the IPL irradiation, the metal layers are broken into nano-islands on CNT due to the surface energy minimization between the metal layers and CNT. The surface characterizations of the Pt-Au/CNT were performed with X-ray diffraction, scanning electron microscope, and energy-dispersive X-ray spectroscopy. Different compositions of alloy nanoparticles were obtained by adjusting the deposition thicknesses of Pt and Au on CNT. Pt50Au50/CNT electrode showed the highest glucose oxidation current peak among Pt, Pt70Au30, Pt50Au50, Pt30Au70, and Au/CNT electrodes while the electroactive surface areas of them are kept to be similar (average surface area=7.00 cm2, coefficient of variation=0.06). The amperometric response of Pt50Au50/CNT electrode to the glucose concentrations showed a wide linear range up to 24.44 mM with a high detection sensitivity of 10.71 µA mM(-1) cm(-2). Reproducibility and long-term stability of the Pt-Au/CNT electrode were also proven in the experiments.

Carbon nanotube mat as mediator-less glucose sensor electrode.

In this paper, the direct electron transfer of glucose oxidase (GOx) on carbon nanotube (CNT) mat electrode is demonstrated. Because of the electrical conductivity and mechanical strength of CNT mat, it can be used as an electrode as well as a catalyst support. Therefore, the preparation process for the CNT mat based sensor electrode is simpler than that of the conventional CNT dispersed sensor electrodes. GOx was covalently immobilized on the oxidized CNT mat, which is connected to a wire by using silver paste and epoxy glue. Attenuated Total Reflectance Fourier Transform-Infrared (ATR-FTIR) result shows transmittance peaks at 1637 cm(-1) and 1525 cm(-1) which are corresponding to the band I and II of amide. Cyclic voltammetric shows a pair of well-defined redox peaks with the average formal potential of -0.425 V (vs. Ag/AgCl reference electrode) in the phosphate buffered saline solution (1 x PBS, pH 7.4). Calculated electron transfer rate constant and the surface density of GOx were 1.71 s(-1) and (3.27 +/- 0.20) x 10(-13) mol/cm2, respectively. Cyclic voltammograms of GOx-CNT mat in glucose solution show that the immobilized GOx retains its catalytic activity to glucose. The amperometric sensor response showed a linear dependence on the glucose concentration in the range of 0.2 mM to 2.18 mM with a detection sensitivity of 4.05 microA mM(-1) cm(-2). The Michaelis-Menten constant of the immobilized GOx was calculated to be 2.18 mM.

Carbon nanotubes with platinum nano-islands as glucose biofuel cell electrodes.

A novel method using intense pulsed light (IPL) for the metal nano-island formation on carbon nanotube (CNT) was introduced. The IPL-induced photothermal dewetting process improved platinum (Pt) catalyst utilization by transforming nano-islands from Pt film on CNT and increasing the surface area for the subsequent sputtering. The irradiation of high intensity of light on the Pt film causes surface-energy-driven diffusion of Pt atoms and forms the array of nano-islands on CNT. The thickness of Pt film can change the size of nano-islands. Cyclic voltammetry showed a dramatically improved glucose oxidation at the IPL morphology modified Pt-CNT electrode compared to the Pt sputtered CNT electrode without IPL irradiation. The power densities of glucose/air biofuel cell based on the morphology modified Pt-CNT electrode and the as-sputtered Pt-CNT electrode were 0.768 microW/cm(2) and 0.178 microW/cm(2), respectively. The biofuel cell based on morphology modified Pt-CNT electrode showed highly stable output in long-term performance. The power density dropped 14.1% in 30 days. Efforts are underway to improve the interface transfer to achieve higher potential and current output.