Single-molecule photobleaching probes the exciton wave function in a multichromophoric system

Ajuts: This work has been supported by the EC Program IHP- 99 (HPMF-CT-2002-01698)The exciton wave function of a trichromophoric system is investigated by means of single molecule spectroscopy at room temperature. Individual trimers exhibit superradiance and loss of vibronic structure in emission spectrum, features proving exciton delocalization. We identify two distinct photodegradation pathways for single trimers upon sequential photobleaching of the chromophores. The rate of each pathway is a measure for the contribution of the separate dyes to the collective excited state of the system, in this way probing the wave function of the delocalized exciton

Energy transfer in single molecular photonic wires

Molecular photonics is a new emerging field of research around the premise that it is possible to develop optical devices using single molecules as building blocks. Truly technological impact in the field requires focussed efforts on designing functional molecular devices as well as having access to their photonic properties on an individual basis. In this Minireview we discuss our approach towards the design and single-molecule investigation of one-dimensional multimolecular arrays intended to work as molecular photonic wires. Three different schemes have been explored: a) perylene-based dimer and trimer arrays displaying coherent exciton delocalisation at room temperature; b) DNA-based unidirectional molecular wires containing up to five different chromophores and exhibiting weak excitonic interactions between neighbouring dyes; and c) one-dimensional multichromophoric polymers based on perylene polyisocyanides showing excimerlike emission. As a whole, our single-molecule data show the importance of well-defined close packing of chromophores for obtaining optimal excitonic behaviour at room temperature. Further improvement on (bio)chemical synthesis, together with the use of single-molecule techniques, should lead in the near future to efficient and reliable photonic wires with true device functionality

Metallo-dielectric diamond and zinc-blende photonic crystals

It is shown that small inclusions of a low absorbing metal can have a dramatic effect on the photonic band structure. In the case of diamond and zinc-blende photonic crystals, several complete photonic band gaps (CPBG's) can open in the spectrum, between the 2nd-3rd, 5th-6th, and 8th-9th bands. Unlike in the purely dielectric case, in the presence of small inclusions of a low absorbing metal the largest CPBG for a moderate dielectric constant (epsilon<=10) turns out to be the 2nd-3rd CPBG. The 2nd-3rd CPBG is the most important CPBG, because it is the most stable against disorder. For a diamond and zinc-blende structure of nonoverlapping dielectric and metallo-dielectric spheres, a CPBG begins to decrease with an increasing dielectric contrast roughly at the point where another CPBG starts to open--a kind of gap competition. A CPBG can even shrink to zero when the dielectric contrast increases further. Metal inclusions have the biggest effect for the dielectric constant 2<=epsilon<=12, which is a typical dielectric constant at near infrared and in the visible for many materials, including semiconductors and polymers. It is shown that one can create a sizeable and robust 2nd-3rd CPBG at near infrared and visible wavelengths even for a photonic crystal which is composed of more than 97% low refractive index materials (n<=1.45, i.e., that of silica glass or a polymer). These findings open the door for any semiconductor and polymer material to be used as genuine building blocks for the creation of photonic crystals with a CPBG and significantly increase the possibilities for experimentalists to realize a sizeable and robust CPBG in the near infrared and in the visible. One possibility is a construction method using optical tweezers, which is analyzed here.Comment: 25 pp, 23 figs, RevTex, to appear in Phys Rev B. For more information look at http://www.amolf.nl/research/photonic_materials_theory/moroz/moroz.htm

Capillary Condensation and Interface Structure of a Model Colloid-Polymer Mixture in a Porous Medium

We consider the Asakura-Oosawa model of hard sphere colloids and ideal polymers in contact with a porous matrix modeled by immobilized configurations of hard spheres. For this ternary mixture a fundamental measure density functional theory is employed, where the matrix particles are quenched and the colloids and polymers are annealed, i.e. allowed to equilibrate. We study capillary condensation of the mixture in a tiny sample of matrix as well as demixing and the fluid-fluid interface inside a bulk matrix. Density profiles normal to the interface and surface tensions are calculated and compared to the case without matrix. Two kinds of matrices are considered: (i) colloid-sized matrix particles at low packing fractions and (ii) large matrix particles at high packing fractions. These two cases show fundamentally different behavior and should both be experimentally realizable. Furthermore, we argue that capillary condensation of a colloidal suspension could be experimentally accessible. We find that in case (ii), even at high packing fractions, the main effect of the matrix is to exclude volume and, to high accuracy, the results can be mapped onto those of the same system without matrix via a simple rescaling.Comment: 12 pages, 9 figures, submitted to PR

Loss of SMAD4 Alters BMP Signaling to Promote Colorectal Cancer Cell Metastasis via Activation of Rho and ROCK

Imaging- and therapeutic targets in neoplastic and musculoskeletal inflammatory diseas

Subnanometer-accuracy optical distance ruler based on fluorescence quenching by transparent conductors

Available data: Complex refractive index of Indium Tin Oxide, http://dx.doi.org/10.4121/uuid:59febf27-a532-4ac9-8ec0-29d4195b2c8c Transparent conductive oxides (TCOs), such as the well-known indium-tin oxide, find widespread use in modern (nano)technological applications because of their unique combination of negligible optical absorption and good electric conductivity. We, however, show that despite the near-zero imaginary part of the refractive index that is responsible for the material’s transparency, TCOs drastically quench optical emitters when the emitter is within 10 nm from the TCO. Our results reveal that the pure near-field nature of this dissipation makes for an exquisite short-range optical ruler. Previous quenching-based optical rulers, based on interactions with plasmonic or graphene materials, have allowed measuring distances in the 20–100 nm range. Distances below 20 nm have, however, been hard to assess due to poor photon yields or weak absolute variations. We show that TCO-based rulers close this gap, allowing distance measurements with far-field optics in the 1–10 nm distance range with deep subnanometer sensitivity.ImPhys/Imaging PhysicsApplied Science

Power-Law Blinking in the Fluorescence of Single Organic Molecules

The blinking behavior of perylene diïmide molecules is investigated at the single-molecule level. We observe long-time scale blinking of individual multi-chromophoric complexes embedded in a poly(methylmethacrylate) matrix, as well as for the monomeric dye absorbed on a glass substrate at ambient conditions. In both these different systems, the blinking of single molecules is found to obey analogous power-law statistics for both the on and off periods. The observed range for single-molecular power-law blinking extends over the full experimental time window, covering four orders of magnitude in time and six orders of magnitude in probability density. From molecule to molecule, we observe a large spread in off-time power-law exponents. The distributions of off-exponents in both systems are markedly different whereas both on-exponent distributions appear similar. Our results are consistent with models that ascribe the power-law behavior to charge separation and (environment-dependent) recombination by electron tunneling to a dynamic distribution of charge acceptors. As a consequence of power-law statistics, single molecule properties like the total number of emitted photons display non-ergodicity