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Christopher J Bardeen

Publications and source records attributed to Christopher J Bardeen.

At least 19 recordsLinked to original sources
PubMed2006

Photochemically driven shape changes of crystalline organic nanorods.

Nanorods composed of 9-tert-butylanthroate (9-TBAE) are synthesized using an Al2O3 template and solvent annealing. The rods consist of micron-scale crystalline domains, and UV light induces a [4 + 4] photodimerization that results in a uniform 15% expansion along the rod axis. This is in contrast to random 9-TBAE crystals, which disintegrate under the same conditions. Transmission electron microscopy, atomic force microscopy, and comparison of the X-ray crystal structures of the monomer and photodimer all provide evidence for a mechanism based on a crystal-to-crystal photoreaction leading to an increase in molecular volume. It is likely that the high surface-to-volume ratio in the nanorods provides a strain relief pathway that is absent in larger crystals. Preliminary attempts to reverse the reaction using shorter wavelength light to photodissociate the dimers were only partly successful. These results suggest that crystalline organic nanostructures may provide an efficient way to transform photochemical energy into mechanical motion on the nanometer scale.

Journal Article↗
PubMed2006

Energy and charge transfer dynamics in fully decorated benzyl ether dendrimers and their disubstituted analogues.

We examine the photophysics of a series of molecules consisting of a benzthiadiazole core surrounded by a network of benzyl ether arms terminated by aminopyrene chromophores, which function as both energy and electron donors. Three classes of molecules are studied: dendrimers whose peripheries are fully decorated with aminopyrene donors (F), disubstituted dendrimers whose peripheries contain only two donors (D), and linear analogues in which a pair of benzyl ether arms link two donors to the central core (L). The electronic energy transfer (EET) and charge transfer (CT) rates are determined by fluorescence lifetime measurements on the energy donors and electron acceptors, respectively. In all three types of molecules, the EET time scales as the square root of the generation number G, consistent with the flexible nature of the benzyl ether framework. Transient anisotropy measurements confirm that donor-donor energy hopping does not play a major role in determining the EET times. The CT dynamics occur on the nanosecond time scale and lead to stretched exponential decays, probably due to conformational disorder. Measurements at 100 degrees C confirm that conformational fluctuations play a role in the CT dynamics. The average CT time increases with G in the L and D molecules but decreases for the F dendrimers. This divergent behavior as G increases is attributed to the competing effects of larger donor-acceptor distances (which lengthen the CT time) versus a larger number of donors (which shorten the average CT time). This work illustrates two important points about light-harvesting and charge-separation dendrimers. First, the use of a flexible dendrimer framework can lead to a more favorable scaling of the EET time (and thus the light-harvesting efficiency) with dendrimer size, relative to what would be expected for a fully extended dendrimer. Second, fully decorated dendrimers can compensate for the distance-dependent slowdown in CT rate as G increases by providing additional pathways for the CT reaction to occur.

Journal Article↗
PubMed2006

Light-harvesting in carbonyl-terminated phenylacetylene dendrimers: The role of delocalized excited States and the scaling of light-harvesting efficiency with dendrimer size.

The photophysics of a family of conjugated phenylacetylene (PA) light-harvesting dendrimers are studied using steady-state and time-resolved optical spectroscopy. The dendrimers consist of a substituted PA core surrounded by meta-branched PA arms. The total number of PA moieties ranges from 3 (first generation) to 63 (fifth generation). By using an alcohol/ketone substituent at the dendrimer core, we avoid through-space Forster transfer from the peripheral PA donors to the core acceptor (in this case, the carbonyl group), which simplifies the analysis of these molecules relative to the perylene-terminated molecules studied previously. The delocalized excited states previously identified in smaller dendrons are seen in these larger dendrimers as well, and their influence on the intersite electronic energy transfer (EET) is analyzed in terms of a point-dipole Forster model. We find that these new delocalized states can both enhance EET (by decreasing the spatial separation between donor and acceptor) and degrade it (by lowering the emission cross section and shifting the energy, resulting in poorer spectral overlap between donor and acceptor). The combination of these two effects leads to a calculated intersite transfer time of 6 ps, in reasonable agreement with the 5-17 ps range obtained from experiment. In addition to characterizing the electronic states and intersite energy transfer times, we also examine how the overall light-harvesting efficiency scales with dendrimer size. After taking the size dependence of other nonradiative processes, such as excimer formation, into account, the overall dendrimer quenching rate k(Q) is found to decrease exponentially with dendrimer size over the first four generations. This exponential decrease is predicted by simple theoretical considerations and by kinetic models, but the dependence on generation is steeper than expected based on those models, probably due to increased disorder in the larger dendrimers. We discuss the implications of these results for dendrimeric light-harvesting structures based on PA and other chemical motifs.

Journal Article↗
PubMed2006

Sunscreen enhancement of UV-induced reactive oxygen species in the skin.

The number of UV-induced (20 mJ cm(-2)) reactive oxygen species (ROS) generated in nucleated epidermis is dependent upon the length of time the UV filter octocrylene, octylmethoxycinnamate, or benzophenone-3 remains on the skin surface. Two-photon fluorescence images acquired immediately after application of each formulation (2 mg cm(-2)) to the skin surface show that the number of ROS produced is dramatically reduced relative to the skin-UV filter control. After each UV filter remains on the skin surface for t=20 min, the number of ROS generated increases, although it remains below the number generated in the control. By t=60 min, the filters generate ROS above the control. The data show that when all three of the UV filters penetrate into the nucleated layers, the level of ROS increases above that produced naturally by epidermal chromophores under UV illumination.

Humans↗
PubMed2006

Dendrimer analogues of linear molecules to evaluate energy and charge-transfer properties.

[reaction: see text] We have designed and synthesized difunctionalized dendrimers containing two donors in the periphery and an acceptor at the core to serve as scaffolds for comparison with linear analogues to investigate the advantage of dendritic scaffolds for energy and charge transfer. Comparison of these dendrimers with the fully decorated dendrimers provides information on the advantage of chromophore density in energy/charge transfer from periphery to the core.

Journal Article↗
PubMed2006

The photophysical properties of chromophores at high (100 mM and above) concentrations in polymers and as neat solids.

The absorption, fluorescence, and photostability of five conjugated chromophores: perylene, 2,5,8,11-tetra-t-butyl perylene (TTBP), perylene orange (PO), perylene red (PR), and a zwitterionic Meisenheimer complex (MHC), are studied as a function of concentration in poly(methyl methacrylate) (PMMA). At 1 mM concentrations, all five molecules exhibit properties consistent with unaggregated chromophores. At higher concentrations, perylene and PO both exhibit excimer formation, while TTBP, PR, and the MHC retain their monomeric fluorescent lineshapes. In these three molecules, however, the fluorescence decay times decrease by 10% (TTBP) to 50% (MHC) at concentrations of 100 mM in PMMA. The fluorescence properties of these highly concentrated samples are sensitive to the sample preparation conditions. In the neat solid where the effective concentration is on the order of 1 M, all three molecules exhibit very fast fluorescence decays, on the order of 150 ps or less, despite the fact that they retain their basic monomeric fluorescence lineshape. In addition to the enhanced nonradiative decay at high concentrations, these three molecules also undergo a concentration-dependent photobleaching. The combined effects of intermolecular nonradiative decay channels and photobleaching appear to be a general obstacle to achieving highly concentrated dye-doped solids.

Computer Simulation↗
PubMed2006

Light harvesting dendrimers.

Tree-like dendrimers with decreasing number of chromophores from periphery to core is an attractive candidate for light-harvesting applications. Numerous dendritic designs with different kinds of light-collecting chromophores at periphery and an energy-sink at the core have been demonstrated with high energy transfer efficiency. These building blocks are now being developed for several applications such as light-emitting diodes, frequency converters and other photonic devices. This review outlines the efforts that are based on both conjugated and non-conjugated dendrimers.

Dendrimers↗
PubMed2006

Using perylene-doped polymer nanotubes as fluorescence sensors.

Al(2)O(3) filters (200 nm) are used as templates to form polymer nanotubes containing an energy donor (perylene). The perylene is isolated from chemical interactions but can undergo electronic energy transfer to acceptor molecules in aqueous solutions passing through the membrane. This energy transfer is analyzed quantitatively in terms of both radiative and nonradiative (Forster transfer) mechanisms and provides a way for the chemically inert filter to sense the presence of analyte molecules in the filtrate.

Energy Transfer↗
PubMed2005

Using meta conjugation to enhance charge separation versus charge recombination in phenylacetylene donor-bridge-acceptor complexes.

A pair of donor-bridge-acceptor electron-transfer complexes, with a carbazole donor and a naphthalimide acceptor connected by either a para- or meta-conjugated phenylacetylene bridge, are synthesized and studied using time-resolved and steady-state spectroscopy. These experiments show that the charge separation times, which depend on the coupling of the donor and acceptor through the excited bridge moiety, are similar for the two molecules (Meta and Para). The charge recombination time, however, is a factor of 10 slower for Meta than for Para. These results are related to changes in the electronic coupling of the bridge depending on its electronic state, and show that meta-conjugated bridges provide a possible motif for the design of asymmetric molecular wires.

Journal Article↗
PubMed2005

Dependence of the two-photon absorption cross section on the conjugation of the phenylacetylene linker in dipolar donor-bridge-acceptor chromophores.

The nonlinear optical properties of four isomeric dipolar two-photon chromophores are compared. The chromophores consist of a carbazole electron donor coupled to a naphthalimide electron acceptor by a phenylacetylene bridge. By variation of the connectivity of the bridge at the phenyl groups, four compounds with 0, 1, and 2 meta linkages are synthesized. The linear and nonlinear optical properties of these compounds are measured. Despite similar linear absorption cross sections, the two-photon absorption cross section delta of the all-meta compound is almost a factor of 10 lower than the all-para compound. By taking the detailed molecular conformations into account in order to calculate accurate dipole moment changes, we find that the decrease in delta results largely from the decreased charge transfer ability with increasing number of meta linkages. We find that a two-state model can be used to predict semiquantitatively the observed trend in delta on the basis of the linear optical properties of the molecules. This work illustrates the dramatic effect the ground-state polarizability can have on the nonlinear optical response of organic compounds and also provides a way to quantify the ability of meta linkages to inhibit charge transfer in their ground-state configuration.

Acetylene↗
PubMed2005

Effects of sonication on the size and crystallinity of stable zwitterionic organic nanoparticles formed by reprecipitation in water.

Nanoparticles of a novel organic zwitterionic Meisenheimer complex, N',N' ',N' ''-tri(isopropyl)-4-oxo-6-(isopropyliminio)-2-s-(2H)triazinespiro-1'-2',4',6'-trinitrocyclohexadienylide, were synthesized by reprecipitation in water under different conditions. While reprecipitation alone resulted in a suspension of amorphous particles that fell out of solution within hours, sonication for different periods of time resulted in the formation of crystalline particles that were stable in solution over the course of weeks. The disk-shaped particles had an average diameter of 140 nm and a thickness of 70 nm. Comparison of the optical spectroscopy of these particles with the monomer indicates that they possess delocalized excitonic states and enhanced radiative decay rates. The use of zwitterionic molecules in conjunction with sonication provides a way to exert some level of control over particle size and morphology, as well as increased colloidal stability.

Journal Article↗
PubMed2005

Effect of guest molecule flexibility in access to dendritic interiors.

[structure: see text] Dendrimers are attractive scaffolds for catalysis, since catalytic sites can be isolated and the catalysts are recoverable and reusable. Herein, we show that conformationally constrained molecules have better access to dendritic cores compared to the more flexible counterparts. The results reported here should have implications in utilizing dendrimers as scaffolds for artificial selectivity in catalysis.

Catalysis↗
PubMed2005

Probing every layer in dendrons.

Dendrons with a fluorescent probe in a specific location have been synthesized and characterized. Accessibility of guest molecules to each of these layers was then analyzed using an intermolecular photoinduced electron-transfer process. Comparisons of the accessibility among each layer of the dendron and among the generations are provided.

Anthracenes↗
PubMed2005

Energy and electron transfer in bifunctional non-conjugated dendrimers.

Nonconjugated dendrimers, which are capable of funneling energy from the periphery to the core followed by a charge-transfer process from the core to the periphery, have been synthesized. The energy and electron donors involve a diarylaminopyrene unit and are incorporated at the periphery of these dendrimers. The energy and electron acceptor is at the core of the dendrimer, which involves a chromophore based on a benzthiadiazole moiety. The backbone of the dendrimers is benzyl ether based. A direct electron-transfer quenching of the excited state of the periphery or a sequential energy transfer-electron-transfer pathway are the two limiting mechanisms of the observed photophysical properties. We find that the latter mechanism is prevalent in these dendrimers. The energy transfer occurs on a picosecond time scale, while the charge-transfer process occurs on a nanosecond time scale. The lifetime of the charge separated species was found to be in the range of microseconds. Energy transfer efficiencies ranging from 80% to 90% were determined using both steady-state and time-resolved measurements, while charge-transfer efficiencies ranging from 70% to 80% were deduced from fluorescence quenching of the core chromophore. The dependence of the energy and charge-transfer processes on dendrimer generation is analyzed in terms of the backfolding of the flexible benzyl ether backbone, which leads to a weaker dependence of the energy and charge-transfer efficiencies on dendrimer size than would be expected for a rigid system.

Journal Article↗
PubMed2004

The effects of connectivity, coherence, and trapping on energy transfer in simple light-harvesting systems studied using the Haken-Strobl model with diagonal disorder.

The problem of electronic energy transfer in a network of two-level systems coupled to a single trapping site is investigated using a simple Haken-Strobl model with diagonal disorder. The goal is to illustrate how the trapping time T(trap), coherence time T(d), and molecular topology all affect the overall efficiency of a light-harvesting network. Several issues are identified that need to be considered in the design of an optimal energy transfer network, including the dephasing-induced decoupling the trap from the rest of the network, the nonlinear dependence of trapping rate on the coherence time, and the role of network size and connectivity in determining the effect of the coherence time on efficiency. There are two main conclusions from this work. First, there exists an optimum combination of trapping time and coherence time, which will give the most rapid population transfer to the trap. These values are not in general the shortest trapping time and the longest coherence time, as would be expected based on rate equation models and/or simple considerations from previous analytical results derived for the Haken-Strobl model in an infinite system. Second, in the coherent regime, where T(d) is longer than the other relevant timescales, population trapping in a finite system can be suppressed by quantum interference effects, whose magnitude is sensitive to the molecular geometry. Suggestions for possible methods of observing such effects are discussed. These results provide a qualitative framework for quantum coherence and molecular topology into account for the design of covalent light-harvesting networks with high energy transfer efficiencies.

Journal Article↗
PubMed2004

Nonstationary rotational diffusion in room temperature liquids measured by femtosecond three-pulse transient anisotropy.

A femtosecond three-pulse chi((5)) polarization anisotropy experiment is used to examine the time dependence of the rotational diffusion of coumarin 153 in polar liquids. By probing the polarization anisotropy decay at various points during the molecule's excited state lifetime, a time-dependent diffusion coefficient is found in several solvents. This anomalous behavior is consistent with the relaxation of the solvent friction to accommodate the solute's excited state charge distribution. Rotational diffusion times measured immediately after photoexcitation by two-pulse chi((3)) experiments may reflect a nonstationary bath dynamics, rather than the equilibrium friction of the solvent.

Journal Article↗
PubMed2004

Exciton delocalization and superradiance in tetracene thin films and nanoaggregates.

The structure and dynamics of luminescent excitons in tetracene thin films and nanoaggregates are investigated using time-resolved spectroscopy and theoretical calculations. The orientation of tetracene's transition dipole moment along its short molecular axis leads to properties qualitatively different from those observed in aggregates of phenylene-vinylene and thiophene oligomers, despite similar crystal structures. The spectral shape, temperature dependence, and radiative lifetime are consistent with a short-lived superradiant exciton delocalized over approximately 10 tetracene molecules.

Journal Article↗