Biomedical subjects

Garry Rumbles

Publications and source records attributed to Garry Rumbles.

9 recordsLinked to original sources

PubMed2006

Photoinduced charge carrier generation in a poly(3-hexylthiophene) and methanofullerene bulk heterojunction investigated by time-resolved terahertz spectroscopy.

We report on the ultrafast photoinduced charge separation processes in varying compositions of poly(3-hexylthiophene) (P3HT) blended with the electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Through the use of time-resolved terahertz spectroscopy, the time- and frequency-dependent complex photoconductivity is measured for samples with PCBM weight fractions (WPCBM) of 0, 0.2, 0.5, and 0.8. By analysis of the frequency-dependent complex conductivity, both the charge carrier yield and the average charge carrier mobility have been determined analytically and indicate a short (<0.2 nm) carrier mean free path and a suppressed long-range transport that is characteristic of carrier localization. Studies on pure films of P3HT demonstrate that charge carrier generation is an intrinsic feature of the polymer that occurs on the time scale of the excitation light, and this is attributed to the dissociation of bound polaron pairs that reside on adjacent polymer chains due to interchain charge transfer. Both interchain and interfacial charge transfer contribute to the measured photoconductivity from the blended samples; interfacial charge transfer increases as a function of increasing PCBM. The addition of PCBM to the polymer films surprisingly does not dramatically increase the production of charge carriers within the first 2 ps. However, charge carriers in the 0.2 and 0.5 blended films survive to much longer times than those in the P3HT and 0.8 films.

Journal Article↗

PubMed2006

Kinetics of PL quenching during single-walled carbon nanotube rebundling and diameter-dependent surfactant interactions.

The kinetics of single-walled carbon nanotube rebundling have been investigated by photoluminescence (PL) spectroscopy. The rate of loss of PL intensity was measured for 12 different nanotubes in three common aqueous surfactants (sodium dodecyl sulfate, SDS; sodium dodecylbenzene sulfonate, SDBS; and sodium cholate, SC) as the surfactant suspensions were diluted to promote nanotube rebundling, quenching of semiconductor nanotube PL, and precipitation. The rate of PL decay was first-order in the concentration of isolated nanotubes, as expected if surfactant desorption is rate-limiting in the rebundling process. Temperature-dependent measurements permitted an Arrhenius analysis from which diameter-dependent activation energies were determined. SDS was found to have very strong diameter dependence for activation energy, with stronger binding to smaller-diameter nanotubes, whereas SDBS displayed a weaker diameter dependence. SC was found to bind strongly to certain nanotubes and weakly to the (10,2) nanotube. The PL emission red shifted with time after dilution as surfactant desorption proceeded. This effect is attributed to an increase in the micropolarity at the nanotube surface.

Benzenesulfonates↗

PubMed2006

Imaging of resonant quenching of surface plasmons by quantum dots.

In scanning tunneling microscopy (STM), confinement of surface plasmons to the optical cavity formed at the metallic tunneling gap stimulates the emission of light. We demonstrate that quantum dots (QDs) found in such a cavity give rise to discrete, observable transitions in the tunneling luminescence spectrum due to the resonant extinction of the plasmon. The observed resonances represent a fingerprint of the QD and occur at the optical band gap owing to the nearly simultaneous transfer of carriers from both sides of the tunneling gap to the QD. The resonant quenching of surface plasmons enables a new imaging technique, dubbed plasmon resonance imaging, with a spatial resolution potentially similar to that of STM and the energy resolution of optical spectroscopies. This detection and imaging strategy is not restricted to QDs, being of great interest to an entire spectrum of nanostructures, from molecular assemblies and biomolecules to carbon nanotubes.

Journal Article↗

PubMed2006

Excitons in nanoscale systems.

Nanoscale systems are forecast to be a means of integrating desirable attributes of molecular and bulk regimes into easily processed materials. Notable examples include plastic light-emitting devices and organic solar cells, the operation of which hinge on the formation of electronic excited states, excitons, in complex nanostructured materials. The spectroscopy of nanoscale materials reveals details of their collective excited states, characterized by atoms or molecules working together to capture and redistribute excitation. What is special about excitons in nanometre-sized materials? Here we present a cross-disciplinary review of the essential characteristics of excitons in nanoscience. Topics covered include confinement effects, localization versus delocalization, exciton binding energy, exchange interactions and exciton fine structure, exciton-vibration coupling and dynamics of excitons. Important examples are presented in a commentary that overviews the present understanding of excitons in quantum dots, conjugated polymers, carbon nanotubes and photosynthetic light-harvesting antenna complexes.

Light↗

PubMed2006

Versatile derivatives of carbohydrate-binding modules for imaging of complex carbohydrates approaching the molecular level of resolution.

The innate binding specificity of different carbohydrate-binding modules (CBMs) offers a versatile approach for mapping the chemistry and structure of surfaces that contain complex carbohydrates. We have employed the distinct recognition properties of a double His-tagged recombinant CBM tagged with semiconductor quantum dots for direct imaging of crystalline cellulose at the molecular level of resolution, using transmission and scanning transmission electron microscopy. In addition, three different types of CBMs from families 3, 6, and 20 that exhibit different carbohydrate specificities were each fused with either green fluorescent protein (GFP) or red fluorescent protein (RFP) and employed for double-labeling fluorescence microscopy studies of primary cell walls and various mixtures of complex carbohydrate target molecules. CBM probes can be used for characterizing both native complex carbohydrates and engineered biomaterials.

Carbohydrate Metabolism↗

PubMed2005

Quenching of semiconductor quantum dot photoluminescence by a pi-conjugated polymer.

In this communication we discuss the possibility of hole transfer between a photoexcited semiconductor quantum dot and a pi-conjugated polymer. This charge-transfer event will be investigated (exploited) on the basis of its implication toward a solar energy conversion scheme. Experimentally, we show that the steady-state photoluminescence (PL) of a solution of InP quantum dots is quenched by the introduction of solvated poly(3-hexylthiophene). Time-resolved PL experiments on these solutions are also presented. It was observed that the PL transients did not significantly change upon the addition of the conductive polymer. These new results indicate that said PL quenching is static in nature. This suggests that in solution, the quantum dot and the polymer exhibit a strong intermolecular interaction. As the two species encounter each other through diffusion, the polymer quenches the quantum dot photoluminescence without altering the population's PL lifetime. This new evidence suggests that the polymer and the quantum dot form a relatively stable complex.

Journal Article↗

PubMed2005

Influence of fluorescence reabsorption and trapping on solid-state optical cooling.

We analyze the random process of fluorescence reabsorption and trapping in solid-state optical materials in general and its influence on the efficiency of optical cooling of solids by anti-Stokes fluorescence in particular. Using the absorption and fluorescence spectra of Yb3+:ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) as input data, we employ a random-walk model to test analytical approximations of the fluorescence escape efficiency and cooling efficiency, including reflections at the boundary.

Journal Article↗

PubMed2005

Direct imaging of surface-enhanced Raman scattering in the near field.

By using near-field scanning microscopy/spectroscopy, we show that surface-enhanced Raman scattering (SERS) of rhodamine 6G deposited on self-affine silver colloidal film is localized to small, down to less than 200 nm, portions of the film. The locus of the SERS signals ("hot spots") does not necessarily reside in special topographic elements such as interstices and between nanoparticles. The local SERS enhancement is estimated to be over 3 orders of magnitude higher compared to the far-field measurements. Near-field imaging of SERS directly validates the theory of the optical response of self-affine fractal objects.

Letter↗

PubMed2002

Peripherally metalated secoporphyrazines: a new generation of photoactive pigments.

Base-catalyzed cross condensation of dipropylmaleonitrile 1 with bis(dimethylamino)maleonitrile 2 in an equimolar ratio afforded the porphyrazines 3a, 4a, 5a, 6a and 7a. Subsequent demetalation of 5a with TFA followed by remetalation with Zn(OAc)(2) gave ligand 5c in good yield. Compound 5c was, in turn, selectively oxidized and further peripherally functionalized using Pt(PhCN)(2)Cl(2) and PdCl(2) to yield the novel seco solitaire porphyrazines 10a and 10b. The photophysical profiles of the seco solitaire porphyrazines 10a and 10b were evaluated by means of absorption, emission, and transient absorption spectroscopy. The new pigments 10a and 10b were found to be photochemically more stable than the solitaire complexes 3d and 3e and mediated the generation of singlet oxygen with quantum yields of 0.59 and 0.45, respectively.

Journal Article↗