Duncan W. McBranch

Nature of the primary photoexcitations in poly(arylene-vinylenes)

Abstract We present an overview of the optical properties and related experimental results obtained from poly( para -phenylene vinylene), PPV, and its soluble derivatives, and we critically examine the interpretation of these data in the context of both the band model and the exciton model of the electronic structure of these semiconducting and luminescent polymers. Results obtained from highly oriented and structurally ordered PPVs demonstrate that the observed disparities between the physical properties of PPV and the polydiacetylenes (PDAs) are not due to disorder; these differences are intrinsic and arise from the fundamental difference in the nature of the low energy photoexcited states: excitons in the PDAs and free carriers in the PPVs.

Surfactant-induced modification of quenching of conjugated polymer fluorescence by electron acceptors: applications for chemical sensing

Abstract Both the photophysics and the fluorescence quenching behavior of an anionic conjugated polymer towards various small molecule quenchers can be modulated effectively by complexing the polymer with a simple countercharged detergent. For example upon adding odecyltrimethylammonium bromide (DTA) to the polymer, cationic quenchers such as methyl viologen become less effective while the quenching by neutral reagents – most notably nitroaromatics or cyanoaromatics – is enhanced. Thus, the polymer–detergent complex provides a new platform for sensing chemical agents via fluorescence quenching. Thin films formed from the complex exhibit high sensitivity to quenching by nitroaromatic vapor and reasonable reversibility.

Building highly sensitive dye assemblies for biosensing from molecular building blocks

Fluorescence superquenching is investigated for polyelectrolytes consisting of cyanine dye pendant polylysines ranging in number of polymer repeat units (NPRU) from 1 to 900, both in solution and after adsorption onto silica nanoparticles. As NPRU increases, the absorption and fluorescence evolve from monomer spectra to red-shifted features indicative of molecular J aggregates. In solution, the superquenching sensitivity toward an anionic electron acceptor increases by more than a millionfold over the NPRU range from 1 to 900. The dramatic increase is attributed to enhanced equilibrium constants for binding the quenchers, and the amplified quenching of a delocalized exciton of ≈100 polymer repeat units. The self-assembly of monomer onto silica and clay nanoparticles leads to formation of J aggregates, and surface-activated superquenching enhanced 10,000× over the monomer in solution, indicating the formation of “self-assembled polymers” on the nanoparticle surface. Utilization of these self-assembled polymers as high-sensitivity biosensors is demonstrated.

Femtosecond high-sensitivity, chirp-free transient absorption spectroscopy using kilohertz lasers.

A simple method is demonstrated for high-sensitivity, chirp-free measurements of femtosecond (fs) transient absorption over the entire bandwidth of a white-light continuum probe. This technique uses phase-sensitive detection, with spectral scanning and simultaneous adjustment of the time delay between pump and probe pulses; it permits a direct measurement of spectra undistorted by chirp at all time scales, limited only by the resolution of the fs source. The method is applied to study the ultrafast relaxation dynamics of pi-conjugated oligomers and semiconductor nanocrystals.

Initial carrier relaxation dynamics in ion-implanted Si nanocrystals: Femtosecond transient absorption study

Transient absorption spectra of ion-implanted Si nanocrystals (NCs) exhibit two picosecond photoinduced absorption features, attributed to carriers in NC quantized states (high-energy band) and Si/SiO2 interface states (low-energy band). Fast relaxation of the high-energy band indicates that populations of quantized states are short lived and decay on the sub-10-ps time scale due to efficient surface trapping. This shows that the red emission in our samples is not due to carriers in quantized states but rather is a result of deactivation of surface traps.

Enhanced optical limiting in derivatized fullerenes

We have observed enhanced optical limiting behavior in solutions of a derivatized fullerene (phenyl-C(61)-butyric acid cholesteryl ester) from 532 to 700 nm. Transient absorption measurements determined the spectral and temporal regions of interest for optical limiting in C(60) and in C(60) derivatives that are due to a reverse saturable absorption mechanism and predicted enhanced limiting at longer wavelengths. Intensity-dependent transmission measurements made at several wavelengths confirmed these results. The increased solubility and the broadened ground-state absorption of the functionalized C(60) make it suitable for use as an optical limiter in the red and the near infrared.

Applications of fluorescent polymer superquenching to high throughput screening assays for protein kinases.

Protein kinases are involved in the regulation of cellular metabolism, growth, differentiation, and proliferation. Aberrations in their function can lead to diseases such as cancer and inflammation. Protein kinases are therefore possible targets for drug therapies. To address the need for high throughput screening of potential inhibitors, QTL has developed a homogeneous and robust kinase assay for use in multiwell plate format. The QTL Lightspeed fluorescence superquenching-based kinase assays do not require specialized equipment, nor do they involve the use of radioactive hazardous materials or antibodies. QTL Lightspeed kinase assays directly measure the enzymatic activity of the target and do not involve secondary (detector) enzyme. In this article, we compare QTL Lightspeed protein kinase assays using Protein Kinase A, Protein Kinase Balpha/Akt1, and ribosomal S6 kinase-2 as examples with other commercially available kinase kits. Our data show that QTL Lightspeed kinase assays offer significant advantages over the current commercial kits in terms of both sensitivity and performance. The QTL Lightspeed kinase assay also offers a kinetic assay mode where the substrate phosphorylation can be monitored in real-time.

Femtosecond dynamics of excitons in π-conjugated oligomers: the role of intrachain two-exciton states in the formation of interchain species

Abstract We report femtosecond transient absorption results for solutions and thin films of a substituted oligomer of poly(para-phenylene vinylene) performed over wide spectral and pump-intensity ranges. Solutions and films exhibit a photoinduced absorption (PA) band with dynamics matching those of the stimulated emission, demonstrating unambiguously that these features originate from intrachain singlet excitons. Thin films exhibit an additional short-wavelength PA band with pump-independent dynamics, indicating the formation of non-emissive interchain excitons. Correlations in the dynamics of the two PA features, as well as the intensity-dependence, provide strong evidence that the formation of interchain excitons is mediated by intrachain two-exciton states.

Excitations and optical properties of phenylene-based conjugated polymers and oligomers

Abstract We present a combined experimental and theoretical study of the ground and photoexcited optical properties of a model oligomer of PPV, MEH-DSB. Our theoretical picture is based upon a band description of electronic states of PPV oligomers, while invoking corrections from Coulomb interactions. The necessary discrete energy levels at low and intermediate energies appear naturally, in addition to the lower energy delocalized states. On this basis we identify the most important features in direct optical absorption for both high (4–6 eV) and low (2–4 eV) photon energies as well as in photoinduced absorption (PA) and stimulated photoemissions (SE) in MEH-DSB solutions, which represent the limit of noninteracting oligomers. While in agreement with previous interpretations for three absorption peaks (2.74, 4.46 and 6.2 eV), we give a new assignment for the most disputed 3.62 eV one as well as for the two PA peaks.

Controlled unidirectional energy transfer in luminescent self-assembled conjugated polymer superlattices

Abstract We report the synthesis and characterization of multi-layered organic superlattices made by polyelectrolyte self-assembly. Self-assembled films were formed from a water-soluble form of poly(phenylene vinylene) with high-photoluminescence quantum efficiency (QE). We observed a self-quenching of the luminescence with increasing film thickness. This quenching can be reversed by inserting spacer layers between each active conjugated layer. A red shift of the luminescence was also observed as additional poly(phenylene vinylene) layers were added. We attribute the red shift and increasing QE to changing polymer conformation, together with efficient unidirectional energy transfer. We rule out quantum confinement as the origin of the red shift.