Postsynthesis stabilization of free-standing mesoporous silica films

Mixed ammonia-water vapor postsynthesis treatment provides a simple and convenient method for stabilizing mesostructured silica films. X-ray diffraction, transmission electron microscopy, nitrogen adsorption/desorption, and solid-state NMR (C-13, Si-29) were applied to study the effects of mixed ammonia-water vapor at 90 degreesC on the mesostructure of the films. An increased cross-linking of the silica network was observed. Subsequent calcination of the silica films was seen to cause a bimodal pore-size distribution, with an accompanying increase in the volume and surface area ratios of the primary (d = 3 nm) to secondary (d = 5-30 nm) pores. Additionally, mixed ammonia-water treatment was observed to cause a narrowing of the primary pore-size distribution. These findings have implications for thin film based applications and devices, such as sensors, membranes, or surfaces for heterogeneous catalysis.

Coherence of polaronic transport in layered metals

Layered systems show anisotropic transport properties. The interlayer conductivity shows a general temperature dependence for a wide class of materials. This can be understood if conduction occurs in two different channels activated at different temperatures. We show that the characteristic temperature dependence can be explained using a polaron model for the transport. The results show an intuitive interpretation in terms of coherent and incoherent quasi-particles within the layers. Further, we extract results for the magnetoresistance, thermopower, spectral function and optical conductivity for the model and discuss application to experiments.

Tailored conductivity in ion implanted polyetheretherketone

Ion implantation can be used to confer electrical conductivity upon conventional insulating polymers such as polyetheretherketone (PEEK). We have implanted PEEK films using three different types of ion implantation: conventional inert gas and metal ion implantation, and ion beam mixing. We have applied a number of analytical techniques to compare the chemical, structural and electrical properties of these films. The most effective means of increasing electrical conductivity appears to be via ion beam mixing of metals into the polymer, followed by metal ion implantation and finally, inert gas ion implantation. Our results suggest that in all cases, the conducting region corresponds to the implanted layer in the near surface to a depth of similar to750 Angstrom (ion beam mixed) to similar to5000 Angstrom (metal ion). This latter value is significantly higher than would be expected from a purely ballistic standpoint, and can only be attributed to thermal inter-diffusion. Our data also indicates that graphitic carbon is formed within the implant region by chain scission and subsequent cross-linking. All ion implanted samples retained their bulk mechanical properties, i.e. they remained flexible. The implant layers showed no signs of de-lamination. We believe this to be the first comparative study between different implantation techniques, and our results support the proposition that soft electronic circuitry and devices can be created by conductivity engineering with ion beams. (C) 2004 Elsevier B.V. All rights reserved.

Localized heating or cooling in mesoscopic devices by electron transport

We describe a method to produce local heating or cooling (depending on how the system is tuned) in a mesoscopic device by transport of electrons. The mechanism can operate on molecules or quantum dots, or any system where the local modes are coupled to vibrations. We believe this will be of future interest in micro electro mechanical systems (MEMS). The amount of heating/cooling obtained depends on the details of the device. We also perform a numerical calculation to display the effect. (C) 2004 Elsevier B.V. All rights reserved.

Growing semiconductor nanocrystals directly in a conducting polymer

We describe a single step method to synthesise lead sulphide (PbS) nanocrystals directly in the conjugated polymer poly (2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV). This method allows size control of the nanocrystal via co-solvent ratios. We find good agreement between nanocrystal sizes determined by transmission electron microscopy and sizes theoretically determined from the absorption edge of the nanocrystals. Finally we show that this synthesis technique is not restricted to MEH-PPV and demonstrate that nanocrystals can be grown in Poly(3-hexylthiophene-2,5-diyl) (P3HT). (C) 2005 Elsevier B.V. All rights reserved.

Determination of thermal and optical parameters of melanins by photopyroelectric spectroscopy

Photopyroelectric spectroscopy (PPE) was used to study the thermal and optical properties of melanins. The photopyroelectric intensity signal and its phase were independently measured as a function of wavelength and chopping frequency for a given wavelength in the saturation part of the PPE spectrum. Equations for both the intensity and the phase of the PPE signal were used to fit the experimental results. From these fits we obtained for the first time, with great accuracy, the thermal diffusivity coefficient, the thermal conductivity, and the specific heat of the samples, as well as a value for the condensed phase optical gap, which we found to be 1.70 eV. (c) 2005 American Institute of Physics.

Lead sulfide nanocrystal: conducting polymer solar cells

In this paper, we report photovoltaic devices fabricated from lead sulfide nanocrystals and the conducting polymer poly(2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylene vinylene). This composite material was produced via a new single-pot synthesis which solves many of the issues associated with existing methods. Our devices have white light power conversion efficiencies under AM 1.5 illumination of 0.7% and single wavelength conversion efficiencies of 1.1%. Additionally, they exhibit remarkably good ideality factors (n = 1.15). Our measurements show that these composites have significant potential as soft optoelectronic materials.

Quantitative photoluminescence of broad band absorbing melanins: a procedure to correct for inner filter and re-absorption effects

We report methods for correcting the photoluminescence emission and excitation spectra of highly absorbing samples for re-absorption and inner filter effects. We derive the general form of the correction, and investigate various methods for determining the parameters. Additionally, the correction methods are tested with highly absorbing fluorescein and melanin (broadband absorption) solutions; the expected linear relationships between absorption and emission are recovered upon application of the correction, indicating that the methods are valid. These procedures allow accurate quantitative analysis of the emission of low quantum yield samples (such as melanin) at concentrations where absorption is significant. (c) 2004 Elsevier B.V. All rights reserved.

Spin boson models for quantum decoherence of electronic excitations of biomolecules and quantum dots in a solvent

We give a theoretical treatment of the interaction of electronic excitations (excitions) in biomolecules and quantum dots with the surrounding polar solvent. Significant quantum decoherence occurs due to the interaction of the electric dipole moment of the solute with the fluctuating electric dipole moments of the individual molecules in the solvent. We introduce spin boson models which could be used to describe the effects. of decoherence on the quantum dynamics of biomolecules which undergo light-induced conformational change and on biomolecules or quantum dots which are coupled by Forster resonant energy transfer.

Equivalence between two-mode spin squeezed states and pure entangled states with equal spin

We prove that a pure entangled state of two subsystems with equal spin is equivalent to a two-mode spin-squeezed state under local operations except for a set of bipartite states with measure zero, and provide a counterexample to the generalization of this result to two subsystems of unequal spin.

5,6-Dihydroxyindole-2-carboxylic acid: a first principles density functional study

We report first principles density functional calculations for 5,6-dihydroxyindole-2-carboxylic acid (DHICA) and several oxidised forms. DHICA and 5,6-dihydroxyindole (DHI) are believed to be the basic building blocks of the eumelanins. Our results show that carboxylation has a significant effect on the physical properties of the molecules. In particular, the relative stabilities and the highest occupied molecular orbital-lowest unoccupied molecular orbital gaps (calculated with the DeltaSCF method) of the various redox forms are strongly affected. We predict that, in contrast to DHI, the density of unpaired electrons, and hence the ESR signal, in DHICA is negligibly small. (C) 2004 Elsevier B.V. All rights reserved.

Measurement-based teleportation along quantum spin chains

We examine the teleportation of an unknown spin-1/2 quantum state along a quantum spin chain with an even number of sites. Our protocol, using a sequence of Bell measurements, may be viewed as an iterated version of the 2-qubit protocol of C. H. Bennett et al. [Phys. Rev. Lett. 70, 1895 (1993)]. A decomposition of the Hilbert space of the spin chain into 4 vector spaces, called Bell subspaces, is given. It is established that any state from a Bell subspace may be used as a channel to perform unit fidelity teleportation. The space of all spin-0 many-body states, which includes the ground states of many known antiferromagnetic systems, belongs to a common Bell subspace. A channel-dependent teleportation parameter O is introduced, and a bound on the teleportation fidelity is given in terms of O.

A quantum yield map for synthetic eumelanin

The quantum yield of synthetic eumelanin is known to be extremely low and it has recently been reported to be dependent on excitation wavelength. In this paper, we present quantum yield as a function of excitation wavelength between 250 and 500 nm, showing it to be a factor of 4 higher at 250 nm than at 500 nm. In addition, we present a definitive map of the steady-state fluorescence as a function of excitation and emission wavelengths, and significantly, a three-dimensional map of the specific quantum yield: the fraction of photons absorbed at each wavelength that are subsequently radiated at each emission wavelength. This map contains clear features, which we attribute to certain structural models, and shows that radiative emission and specific quantum yield are negligible at emission wavelengths outside the range of 585 and 385 nm (2.2 and 3.2 eV), regardless of excitation wavelength. This information is important in the context of understanding melanin biofunctionality, and the quantum molecular biophysics therein. (c) 2005 American Institute of Physics.

Optical scatter imaging using digital Fourier microscopy

An approach reported recently by Alexandrov et al (2005 Int. J Imag. Syst. Technol. 14 253-8) on optical scatter imaging, termed digital Fourier microscopy (DFM), represents an adaptation of digital Fourier holography to selective imaging of biological matter. The holographic mode of the recording of the sample optical scatter enables reconstruction of the sample image. The form-factor of the sample constituents provides a basis for discrimination of these constituents implemented via flexible digital Fourier filtering at the post-processing stage. As in dark-field microscopy, the DFM image contrast appears to improve due to the suppressed optical scatter from extended sample structures. In this paper, we present the theoretical and experimental study of DFM using a biological phantom that contains polymorphic scatterers.

Quantitative fluorescence excitation spectra of synthetic eumelanin

Previously reported excitation spectra for eumelanin are sparse and inconsistent. Moreover, these studies have failed to account for probe beam attenuation and emission reabsorption within the samples, making them qualitative at best. We report for the first time quantitative excitation spectra for synthetic eumelanin, acquired for a range of solution concentrations and emission wavelengths. Our data indicate that probe beam attenuation and emission reabsorption significantly affect the spectra even in low-concentration eumelanin solutions and that previously published data do not reflect the true excitation profile. We apply a correction procedure (previously applied to emission spectra) to account for these effects. Application of this procedure reconstructs the expected relationship of signal intensity with concentration, and the normalized spectra show a similarity in form to the absorption profiles. These spectra reveal valuable information regarding the photophysics and photochemistry of eumelanin. Most notably, an excitation peak at 365 urn (3.40 eV), whose position is independent of emission wavelength, is possibly attributable to a 5,6-dihydroxyindole-2-carboxylic acid (DHICA) component singly linked to a polymeric structure.