Zee Hwan Kim

One-Step Synthesis of Au@Pd Core−Shell Nanooctahedron

Octahedral Au@Pd core-shell nanoparticles have been prepared by a one-step aqueous synthesis method where both metal precursors are present simultaneously with the use of cetyltrimethylammonium chloride as both reductant and stabilizer.

Charge Transfer Enhancement in the SERS of a Single Molecule

We measured the surface-enhanced Raman scattering (SERS) of individual gold nanoparticle-4-aminobenzenethiol (ABT)-gold film junctions to investigate the charge-transfer (CT) enhancement of the SERS signals. Despite the mild electromagnetic field enhancement (∼10(5)) and high surface density of the ABT-molecules (∼240 molecules/hotspot) at the junctions, we observed the clear spectral and temporal signatures of CT-enhanced single-molecule SERS (SM-SERS). The result reveals that only a small fraction of the molecules at the junction has a significant CT-enhancement of 10(1)∼10(3), whereas the rest of the molecules are nearly CT-inactive. Furthermore, the result also proves that overall (charge-transfer and electromagnetic) enhancement of 10(6)∼10(8) is sufficient to observe the SM-SERS of an electronically off-resonant molecule, which disproves the widespread belief that a minimum enhancement of ∼10(14) is required for SM-SERS.

Real-Space Mapping of the Strongly Coupled Plasmons of Nanoparticle Dimers

We carried out the near-field optical imaging of isolated and dimerized gold nanocubes to directly investigate the strong coupling between two adjacent nanoparticles. The high-resolution (approximately 10 nm) local field maps (intensities and phases) of self-assembled nanocube dimers reveal antisymmetric plasmon modes that are starkly different from a simple superposition of two monomeric dipole plasmons, which is fully reproduced by the electrodynamics simulations. The result decisively proves that, for the closely spaced pair of nanoparticles (interparticle distance/particle size approximately 0.04), the strong Coulombic attraction between the charges at the interparticle gap dominates over the intraparticle charge oscillations, resulting in a hybridized dimer plasmon mode that is qualitatively different from those expected from a simple dipole-dipole coupling model.

Femtosecond characterization of vibrational optical activity of chiral molecules

Optical activity is the result of chiral molecules interacting differently with left versus right circularly polarized light. Because of this intrinsic link to molecular structure, the determination of optical activity through circular dichroism (CD) spectroscopy has long served as a routine method for obtaining structural information about chemical and biological systems in condensed phases. A recent development is time-resolved CD spectroscopy, which can in principle map the structural changes associated with biomolecular function and thus lead to mechanistic insights into fundamental biological processes. But implementing time-resolved CD measurements is experimentally challenging because CD is a notoriously weak effect (a factor of 10-4–10-6 smaller than absorption). In fact, this problem has so far prevented time-resolved vibrational CD experiments. Here we show that vibrational CD spectroscopy with femtosecond time resolution can be realized when using heterodyned spectral interferometry to detect the phase and amplitude of the infrared optical activity free-induction-decay field in time (much like in a pulsed NMR experiment). We show that we can detect extremely weak signals in the presence of large achiral background contributions, by simultaneously measuring with a femtosecond laser pulse the vibrational CD and optical rotatory dispersion spectra of dissolved chiral limonene molecules. We have so far only targeted molecules in equilibrium, but it would be straightforward to extend the method for the observation of ultrafast structural changes such as those occurring during protein folding or asymmetric chemical reactions. That is, we should now be in a position to produce ‘molecular motion pictures’ of fundamental molecular processes from a chiral perspective.

High-mobility anthracene-based X-shaped conjugated molecules for thin film transistors

New anthracene-based X-shaped conjugated molecules and for use as highly soluble p-type organic semiconductors were developed and exhibited large field-effect mobilities of 0.04 cm(2) V(-1) s(-1) (I(on)/I(off) = 2.8 x 10(5)) and 0.24 cm(2) V(-1) s(-1) (I(on)/I(off) = 5.4 x 10(6)) for devices of and , respectively.

Metal-Catalyzed Chemical Reaction of Single Molecules Directly Probed by Vibrational Spectroscopy

The study of heterogeneous catalytic reactions remains a major challenge because it involves a complex network of reaction steps with various intermediates. If the vibrational spectra of individual molecules could be monitored in real time, one could characterize the structures of the intermediates and the time scales of reaction steps without ensemble averaging. Surface-enhanced Raman scattering (SERS) spectroscopy does provide vibrational spectra with single-molecule sensitivity, but typical single-molecule SERS signals exhibit spatial heterogeneities and temporal fluctuations, making them difficult to be used in single-molecule kinetics studies. Here we show that SERS can monitor the single-molecule catalytic reactions in real time. The surface-immobilized reactants placed at the junctions of well-defined nanoparticle-thin film structures produce time-resolved SERS spectra with discrete, step-transitions of photoproducts. We interpret that such SERS-steps correspond to the reaction events of individual molecules occurring at the SERS hotspot. The analyses of the yield, dynamics, and the magnitude of such SERS steps, along with the associated spectral characteristics, fully support our claim. In addition, a model that is based on plasmonic field enhancement and surface photochemistry reproduces the key features of experimental observation. Overall, the result demonstrates that it is possible, under well-controlled conditions, to differentiate the chemical and physical processes contributing to the single-molecule SERS signals, and thus shows the use of single-molecule SERS as a tool for studying the metal-catalyzed organic reactions.

Stem-piped light activates phytochrome B to trigger light responses in Arabidopsis thaliana roots

Light conducted through plant tissues activates a photoreceptor in the roots of Arabidopsis thaliana. Plant stems pipe light to roots Light affects not only the development and physiology of the shoots (stems, leaves, and flowers) of plants but also the underground root system. Light triggers shoot cells to release signals that travel to the root and affect the development and physiology of the root system. Like shoot cells, root cells also have photoreceptors that can be activated by light, leading Lee et al. to investigate if light actually reaches these underground parts of the plant. Exposing Arabidopsis thaliana shoots to light while protecting the roots from light activated the photoreceptor phyB in the roots. In the root, phyB activated Hy5, a transcription factor that mediates cellular responses to light and was important for growth of the primary root and for root gravitropism, the proper downward orientation of roots. Arabidopsis stems efficiently conducted only certain wavelengths of light to the root tissues, and these conducted wavelengths activated phyB directly in the roots. These findings demonstrate that roots not only receive information about light conditions through signaling molecules that travel from the shoot to the root in response to light but also directly perceive light that is conducted through the plant tissues. The roles of photoreceptors and their associated signaling mechanisms have been extensively studied in plant photomorphogenesis with a major focus on the photoresponses of the shoot system. Accumulating evidence indicates that light also influences root growth and development through the light-induced release of signaling molecules that travel from the shoot to the root. We explored whether aboveground light directly influences the root system of Arabidopsis thaliana. Light was efficiently conducted through the stems to the roots, where photoactivated phytochrome B (phyB) triggered expression of ELONGATED HYPOCOTYL 5 (HY5) and accumulation of HY5 protein, a transcription factor that promotes root growth in response to light. Stimulation of HY5 in response to illumination of only the shoot was reduced when root tissues carried a loss-of-function mutation in PHYB, and HY5 mutant roots exhibited alterations in root growth and gravitropism in response to shoot illumination. These findings demonstrate that the underground roots directly sense stem-piped light to monitor the aboveground light environment during plant environmental adaptation.

Controlled synthesis and characterization of the enhanced local field of octahedral Au nanocrystals

Octahedral Au nanocrystals with localized surface plasmon-assisted enhancing optical properties can be prepared in aqueous solution via the forced reduction of Au ions by ascorbic acid through the addition of NaOH.

Polarization-selective mapping of near-field intensity and phase around gold nanoparticles using apertureless near-field microscopy

Enhanced near-field distributions around a single gold nanosphere are imaged using scattering-type apertureless near field scanning optical microscopy (ANSOM) at a wavelength of 632.8 nm. For the first time, polarization-selected ANSOM images are obtained that show both the transverse (perpendicular to the tip axis) and the longitudinal (parallel to the tip axis) vector components of the near-field in a phase sensitive manner. A model calculation using a Greens dyadic propagator method successfully reproduces the features of the observed intensity and phase images, providing an interpretation of the ANSOM images. The results open up the possibility that the field vector directions as well as the field magnitude around plasmonic nanostructures and nanodevices can be directly mapped using the ANSOM technique.

Fabrication of Si1−xGex alloy nanowire field-effect transistors

The authors present the demonstration of nanowire field-effect transistors incorporating group IV alloy nanowires, Si1−xGex. Single-crystalline Si1−xGex alloy nanowires were grown by a Au catalyst-assisted chemical vapor synthesis using SiH4 and GeH4 precursors, and the alloy composition was reproducibly controlled in the whole composition range by controlling the kinetics of catalytic decomposition of precursors. Complementary in situ doping of Si1−xGex nanowires was achieved by PH3 and B2H6 incorporation during the synthesis for n- and p-type field-effect transistors. The availability of both n- and p-type Si1−xGex nanowire circuit components suggests implications for group IV semiconductor nanowire electronics and optoelectronics.