Orientational Imaging of Subwavelength Au Particles with Higher Order Laser Modes

We present a new method for the imaging of single metallic nanoparticles that provides information about their shape and orientation. Using confocal microscopy in combination with higher order laser modes, scattering images of individual particles are recorded. Gold nanospheres and nonorods render characteristic patterns reflecting the different particle geometries. In the case of nanorods, the scattering patterns also reveal the orientation of the particles. This novel technique provides a promising tool for the visualization of nonbleaching labels in the biosciences

Controlling Nonequilibrium Phonon Populations in Single-Walled Carbon Nanotubes

We studied spatially isolated single-walled carbon nanotubes (SWNTs) immobilized in a quasi-planar optical λ/2-microresonator using confocal microscopy and spectroscopy. The modified photonic mode density within the resonator is used to selectively enhance or inhibit different Raman transitions of SWNTs. Experimental spectra are presented that exhibit single Raman bands only. Calculations of the relative change in the Raman scattering cross sections underline the potential of our microresonator for the optical control of nonequilibrium phonon populations in SWNT

Tip-enhanced Near-Field Optical Spectroscopy on Single-Walled Carbon Nanotubes

High resolution optical methods overcome the diraction limit, a step essential for understanding the physical and chemical properties of nanostructures. In this work, I applied tip-enhanced near-eld optical microscopy (TENOM) to study the optical properties of single-wall carbon nanotubes (SWNTs) with nanoscale spatial resolution. Simultaneously obtained near-eld Raman scattering and photoluminescence (PL) data is shown to provide information with unprecedented detail on the nanotube structure and the resulting phonon and exciton properties. Near-eld PL is found to be more localized along single nanotubes than Raman scattering in most cases due to defects and environmental perturbations. By detecting near-eld PL spectra, my work has shown exciton energy variations along the same nanotubes induced by the environment. The local PL energy response to DNA-wrapping reveals large DNA-induced redshifts of the exciton energy that are two times higher than indicated by spatially averaging confocal microscopy. Exciton energy transfer between two semiconducting nanotubes is observed for the rst time limited to small distances because of competing fast non-radiative relaxation. The transfer mechanism is explained by F�orster-type electromagnetic near-eld coupling. In addition, towards the end of a nanotube, PL decay is observed on a length scale of 15-40 nm which is attributed to exciton propagation followed by additional non-radiative relaxation at the nanotube end. The dierent enhancement mechanisms of Raman scattering and PL lead to dierent enhancement factors of the two signals. The PL enhancement can be stronger than the Raman enhancement because of the very low initial quantum yield of nanotubes. The signal enhancement of Raman scattering and PL is also found to exhibit dierent tip-sample distance dependencies because of the PL quenching eects from the gold tip. The results achieved in my thesis highlight the enormous capabilities of TENOM for the investigation of nanoscale surfaces

Exciton Energy Transfer in Pairs of Single-Walled Carbon Nanotubes

We studied the exciton energy transfer in pairs of semiconducting nanotubes using high-resolution optical microscopy and spectroscopy on the nanoscale. Photoluminescence from large band gap nanotubes within bundles is observed with spatially varying intensities due to distance-dependent internanotube transfer. The range of efficient energy transfer is found to be limited to a few nanometers because of competing fast nonradiative relaxation responsible for low photoluminescence quantum yield

Exponential Decay Lifetimes of Excitons in Individual Single-Walled Carbon Nanotubes

The dynamics of excitons in individual semiconducting single-walled carbon nanotubes was studied using time-resolved photoluminescence (PL) spectroscopy. The PL decay from tubes of the same (n,m) type was found to be monoexponential, however, with lifetimes varying between less than 20 and 200 ps from tube to tube. Competition of nonradiative decay of excitons is facilitated by a thermally activated process, most likely a transition to a low-lying optically inactive trap state that is promoted by a low-frequency phonon mode

Visualizing the Local Optical Response of Semiconducting Carbon Nanotubes to DNA-Wrapping

We studied the local optical response of semiconducting single-walled carbon nanotubes to wrapping by DNA segments using high resolution tip-enhanced near-field microscopy. Photoluminescence (PL) near-field images of single nanotubes reveal large DNA-wrapping-induced red shifts of the exciton energy that are two times higher than indicated by spatially averaging confocal microscopy. Near-field PL spectra taken along nanotubes feature two distinct PL bands resulting from DNA-wrapped and unwrapped nanotube segments. The transition between the two energy levels occurs on a length scale smaller than our spatial resolution of about 15 nm

Raman Spectroscopy of Graphene Edges

Graphene edges are of particular interest since their orientation determines the electronic properties. Here we present a detailed Raman investigation of graphene flakes with edges oriented at different crystallographic directions. We also develop a real space theory for Raman scattering to analyze the general case of disordered edges. The position, width, and intensity of G and D peaks are studied as a function of the incident light polarization. The D-band is strongest for polarization parallel to the edge and minimum for perpendicular. Raman mapping shows that the D peak is localized in proximity of the edge. For ideal edges, the D peak is zero for zigzag orientation and large for armchair, allowing in principle the use of Raman spectroscopy as a sensitive tool for edge orientation. However, for real samples, the D to G ratio does not always show a significant dependence on edge orientation. Thus, even though edges can appear macroscopically smooth and oriented at well-defined angles, they are not necessarily microscopically ordered

Nature of the constant factor in the relation between radial breathing mode frequency and tube diameter for single-wall carbon nanotubes

Resonance Raman scattering is used to determine the radial breathing mode (RBM) frequency (ωRBM) dependence on tube diameter (dt) for single-wall carbon nanotubes (SWNTs). We establish experimentally the ωRBM=227.0/dt as the fundamental relation for pristine SWNTs. All the other RBM values found in the literature can be explained by an upshift in frequency due mostly to van der Waals interaction between SWNTs and environment

Polyurea-Functionalized Multiwalled Carbon Nanotubes

An in situ polycondensation approach was applied to functionalize multiwalled carbon nanotubes (MWNTs), resulting in various linear or hyperbranched polycondensed polymers [e.g., polyureas, polyurethanes, and poly(urea-urethane)-bonded carbon nanotubes]. The quantity of the grafted polymer can be easily controlled by the feed ratio of monomers. As a typical example, the polyurea-functionalized MWNTs were measured and characterized in detail. The oxidized MWNTs (MWNT-COOH) were converted into acyl chloride-functionalized MWNTs (MWNT-COCl) by reaction with neat thionyl chloride (SOCl2). MWNT-COCl was reacted with excess 1,6-diaminohexane, affording amino-functionalized MWNTs (MWNT-NH2). In the presence of MWNT-NH2, the polyurea was covalently coated onto the surfaces of the nanotube by in situ polycondensation of diisocyanate [e.g., 4,4‘-methylenebis(phenylisocyanate)] and 1,6-diaminohexane, followed by the removal of free polymer via repeated filtering and solvent washing. The coated polyurea content can be controlled to some extent by adjusting the feed ratio of the isocyanato and amino groups. The structure and morphology of the resulting nanocomposites were characterized by FTIR, NMR, Raman, confocal Raman, TEM, EDS, and SEM measurements. The polyurea-coated MWNTs showed interesting self-assembled flat- or flowerlike morphologies in the solid state. The signals corresponding to that of the D and G bands of the carbon nanotubes were strongly attenuated after polyurea was chemically tethered to the MWNT surfaces. Comparative experiments showed that the grafted polymer species and structures have a strong effect on the Raman signals of polymer-functionalized MWNTs

DNA Checkpoint and Repair Factors Are Nuclear Sensors for Intracellular Organelle Stresses-Inflammations and Cancers Can Have High Genomic Risks.

Under inflammatory conditions, inflammatory cells release reactive oxygen species (ROS) and reactive nitrogen species (RNS) which cause DNA damage. If not appropriately repaired, DNA damage leads to gene mutations and genomic instability. DNA damage checkpoint factors (DDCF) and DNA damage repair factors (DDRF) play a vital role in maintaining genomic integrity. However, how DDCFs and DDRFs are modulated under physiological and pathological conditions are not fully known. We took an experimental database analysis to determine the expression of 26 DNA D