Hyeon Don Song

Hot-Electron-Transfer Enhancement for the Efficient Energy Conversion of Visible Light†

Great strides have been made in enhancing solar energy conversion by utilizing plasmonic nanostructures in semiconductors. However, current generation with plasmonic nanostructures is still somewhat inefficient owing to the ultrafast decay of plasmon-induced hot electrons. It is now shown that the ultrafast decay of hot electrons across Au nanoparticles can be significantly reduced by strong coupling with CdS quantum dots and by a Schottky junction with perovskite SrTiO3 nanoparticles. The designed plasmonic nanostructure with three distinct components enables a hot-electron-assisted energy cascade for electron transfer, CdS→Au→SrTiO3, as demonstrated by steady-state and time-resolved photoluminescence spectroscopy. Consequently, hot-electron transfer enabled the efficient production of H2 from water as well as significant electron harvesting under irradiation with visible light of various wavelengths. These findings provide a new approach for overcoming the low efficiency that is typically associated with plasmonic nanostructures.

Core–Satellites Assembly of Silver Nanoparticles on a Single Gold Nanoparticle via Metal Ion-Mediated Complex

We report core-satellites (Au-Ag) coupled plasmonic nanoassemblies based on bottom-up, high-density assembly of molecular-scale silver nanoparticles on a single gold nanoparticle surface, and demonstrate direct observation and quantification of enhanced plasmon coupling (i.e., intensity amplification and apparent spectra shift) in a single particle level. We also explore metal ion sensing capability based on our coupled plasmonic core-satellites, which enabled at least 1000 times better detection limit as compared to that of a single plasmonic nanoparticle. Our results demonstrate and suggest substantial promise for the development of coupled plasmonic nanostructures for ultrasensitive detection of various biological and chemical analytes.

Preparation of energy storage material derived from a used cigarette filter for a supercapacitor electrode.

We report on a one-step method for preparing nitrogen doped (N-doped) meso-/microporous hybrid carbon material (NCF) via the heat treatment of used cigarette filters under a nitrogen-containing atmosphere. The used cigarette filter, which is mostly composed of cellulose acetate fibers, can be transformed into a porous carbon material that contains both the mesopores and micropores spontaneously. The unique self-developed pore structure allowed a favorable pathway for electrolyte permeation and contact probability, resulting in the extended rate capability for the supercapacitor. The NCF exhibited a better rate capability and higher specific capacitance (153.8 F g(-1)) compared to that of conventional activated carbon (125.0 F g(-1)) at 1 A g(-1). These findings indicate that the synergistic combination of well-developed meso-/micropores, an enlarged surface area and pseudocapacitive behavior leads to the desired supercapacitive performance. The prepared carbon material is capable of reproducing its electrochemical performance during the 6000 cycles required for charge and discharge measurements.

A biodegradable gel electrolyte for use in high-performance flexible supercapacitors.

Despite the significant advances in solid polymer electrolytes used for supercapacitors, intractable problems including poor ionic conductivity and low electrochemical performance limit the practical applications. Herein, we report a facile approach to synthesize a NaCl-agarose gel electrolyte for use in flexible supercapacitors. The as-prepared agarose hydrogel consists of a three-dimensional chemically interconnected agarose backbone and oriented interparticular submicropores filled with water. The interconnected agarose matrix acts as a framework that provides mechanical stability to the gel electrolyte and hierarchical porous networks for optimized ion transport. The developed pores with the water filler provide an efficient ionic pathway to the storage sites of electrode. With these properties, the gel electrolyte enables the supercapacitor to have a high specific capacitance of 286.9 F g(-1) and a high rate capability that is 80% of specific capacitance obtained in the case of a liquid electrolyte at 100 mV s(-1). In addition, attributed to the simple procedure and its components, the gel electrolyte is highly scalable, cost-effective, safe, and nontoxic. Thus, the developed gel electrolyte has the potential for use in various energy storage and delivery systems.

On-chip colorimetric detection of Cu2+ ions via density-controlled plasmonic core-satellites nanoassembly.

We report on an on-chip colorimetric method for the detection and analysis of Cu(2+) ions via the targeted assembly of plasmonic silver nanoparticles (2.6 nm satellites) on density-controlled plasmonic gold nanoparticles (50 nm cores) on a glass substrate. Without any ligand modification of the nanoparticles, by directly using an intrinsic moiety (carboxylate ion, COO(-)) surrounded with nanoparticles, the method showed a high selectivity for Cu(2+), resulting in a nearly 2 times greater optical response compared to those of other metal ions via the targeted core-satellites assembly. By modulating the surface chemistry, it was possible to control the density of core gold nanoparticles on the surface, thus permitting easy tuning of the optical responses induced by plasmon coupling generated between each core-satellites nanostructure. Using chips with a controlled optimal core density, we observed the remarkable scattering color changes of the chips from green to yellow and finally to orange with the increase of Cu(2+) concentration. The detection limits of the fabricated chips with controlled core densities (ca. 1821 and 3636 particles/100 μm(2)) are 10 nM and 10 pM, respectively, which are quite tunable and below the level of 20 μM (or 1.3 ppm) defined by the United States Environmental Protection Agency. The findings suggest that the method is a potentially promising protocol for detecting small molecules with target selectivity and the tunability of the detection limits by replacing with ligands and adjusting core densities.

Picomolar selective detection of mercuric ion (Hg2 + ) using a functionalized single plasmonic gold nanoparticle

A highly sensitive method for the selective detection and quantification of mercuric ions (Hg(2+)) using single plasmonic gold nanoparticle (GNP)-based dark-field microspectroscopy (DFMS) is demonstrated. The method is based on the scattering property of a single GNP that is functionalized with thiolated molecules, which is altered when analytes bind to the functionalized GNP. The spectral resolution of the system is 0.26 nm and a linear response to Hg(2+) was found in the dynamic range of 100 pM-10 microM. The method permits Hg(2+) to be detected at the picomolar level, which is a remarkable reduction in the detection limit, considering the currently proscribed Environmental Protection Agency regulation level (10 nM, or 2 ppb) and the detection limits of other optical methods for detecting Hg(2+) (recently approx. 1-10 nM). In addition, Hg(2+) can be sensitively detected in the presence of Cd(2+), Pb(2+), Cu(2+), Zn(2+) and Ni(2+), which do not interfere with the analysis. Based on the findings reported herein, it is likely that single-nanoparticle-based metal ion sensing can be extended to the development of other chemo- and biosensors for the direct detection of specific targets in an intracellular environment as well as in environmental monitoring.

Lipid molecules induce the cytotoxic aggregation of Cu/Zn superoxide dismutase with structurally disordered regions

Cu/Zn-superoxide dismutase (SOD1) is present in the cytosol, nucleus, peroxisomes and mitochondrial intermembrane space of human cells. More than 114 variants of human SOD1 have been linked to familial amyotrophic lateral sclerosis (ALS), which is also known as Lou Gehrigs disease. Although the ultimate mechanisms underlying SOD1-mediated cytotoxicity are largely unknown, SOD1 aggregates have been strongly implicated as a common feature in ALS. This study examined the mechanism for the formation of SOD1 aggregates in vitro as well as the nature of its cytotoxicity. The aggregation propensity of SOD1 species was investigated using techniques ranging from circular dichroism spectroscopy to fluorescence dye binding methods, as well as electron microscopic imaging. The aggregation of SOD1 appears to be related to its structural instability. The demetallated (apo)-SOD1 and aggregated SOD1 species, with structurally disordered regions, readily undergo aggregation in the presence of lipid molecules, whereas metallated (holo)-SOD1 does not. The majority of aggregated SOD1s that are induced by lipid molecules have an amorphous morphology and exhibit significant cytotoxicity. The lipid binding propensity of SOD1 was found to be closely related to the changes in surface hydrophobicity of the proteins, even at very low levels, which induced further binding and assembly with lipid molecules. These findings suggest that lipid molecules induce SOD1 aggregation under physiological conditions and exert cytotoxicity, and might provide a possible mechanism for the pathogenesis of ALS.

Simultaneous Optical Monitoring of the Overgrowth Modes of Individual Asymmetric Hybrid Nanoparticles

Nanoparticles that combine domains with different composi-tions (e.g., noble metals, iron oxide, organic compounds, orpolymer) have attracted considerable interest for biomedicalapplications, because two or more important functions, forexample, targeting, imaging, and therapy, can be combinedinto a single nanoparticle, and such a particle would increasethe precision and efficacy of diagnosis and treatment.

Direct Observation of Defects and Increased Ion Permeability of a Membrane Induced by Structurally Disordered Cu/Zn-Superoxide Dismutase Aggregates

Interactions between protein aggregates and a cellular membrane have been strongly implicated in many protein conformational diseases. However, such interactions for the case of Cu/Zn superoxide dismutase (SOD1) protein, which is related to fatal neurodegenerative disorder amyotrophic lateral sclerosis (ALS), have not been explored yet. For the first time, we report the direct observation of defect formation and increased ion permeability of a membrane induced by SOD1 aggregates using a supported lipid bilayer and membrane patches of human embryonic kidney cells as model membranes. We observed that aggregated SOD1 significantly induced the formation of defects within lipid membranes and caused the perturbation of membrane permeability, based on surface plasmon resonance spectroscopy, atomic force microscopy and electrophysiology. In the case of apo SOD1 with an unfolded structure, we found that it bound to the lipid membrane surface and slightly perturbed membrane permeability, compared to other folded proteins (holo SOD1 and bovine serum albumin). The changes in membrane integrity and permeability were found to be strongly dependent on the type of proteins and the amount of aggregates present. We expect that the findings presented herein will advance our understanding of the pathway by which structurally disordered SOD1 aggregates exert toxicity in vivo.

The sensitive, anion-selective detection of arsenate with poly(allylamine hydrochloride) by single particle plasmon-based spectroscopy.

The use of single gold nanoparticle plasmon-based spectroscopy for the sensitive, anion-selective detection of arsenate is described. The method is based on the selective formation of electrostatic complexes between arsenate and poly(allylamine hydrochloride) (PAH) and changes in the single particle plasmon in Rayleigh scattering profiles. PAH, when modified with gold nanoparticles, binds arsenate via its amine-functionalities. The scattering properties of the resulting selectively formed complexes are altered, leading to significant changes in the surface plasmon resonance wavelength. The limit of detection of the method was determined to be 10 nM, which is ca. 13 times more sensitive than U.S. EPA regulation levels. The response is essentially linear in the concentration range of 50-300 nM. The method also shows good selectivity for arsenate in the presence of other environmentally relevant anions, including H(2)PO(4)(-), SO(4)(2-), NO(3)(-), and Cl(-).