Polarisation Sensitive Single Molecule Fluorescence Detection with Linear Polarised Excitation Light and Modulated Polarisation Direction Applied to Multichromophoric Entities

Recently, investigations of the fluorescence properties of a multichromophoric dendritic entity at the single molecule level have revealed multiple fluorescence levels, collective off-states, variations of the polarisation, large shifts in the spectral position and changes in the fluorescence decay time. In order to further elucidate the multiple processes taking place in this entity, measurements were done in which the polarisation direction of the linear polarised excitation light was modulated. The detection was sensitive for the s- and p-components of the emitted light. The patterns of modulation and relative intensity in the acquired traces reflect the energy transfer processes occurring in this multichromophoric molecule. In-phase modulation and no modulation are the typical modulation patterns that were observed. Simulations involving several models for energy transfer between the chromophores have been carried out taking into account identical conditions as for the performed measurements. The comparison of the modulation patterns and polarisation histograms to the measured data rules out certain models and refines the photophysical model for the multichromophoric entity

Raman spectroscopy and electrical properties of InAs nanowires with local oxidation enabled by substrate micro-trenches and laser irradiation

The thermal gradient along indium-arsenide nanowires was engineered by a combination of fabricated micro- trenches in the supporting substrate and focused laser irradiation. This allowed local control of thermally activated oxidation reactions of the nanowire on the scale of the diffraction limit. The locality of the oxidation was detected by micro-Raman mapping, and the results were found consistent with numerical simulations of the temperature profile. Applying the technique to nanowires in electrical devices the locally oxidized nanowires remained conducting with a lower conductance as expected for an effectively thinner conducting core

Conformational rearrangements in and twisting of a single molecule

Single molecule spectroscopy is used to obtain detailed information on the photophysical properties of immobilized perylenediimide-based molecules, substituted in the bay positions. The fluorescence spectra recorded for numerous single molecules show a clear bimodal distribution of the peak position. Within the low energy component of the distribution, two different vibronic shapes of the emission spectrum can be seen, which can be correlated to different decay times. We show that former observation can be explained by conformational changes of the bay substituents while the latter are related to twisting of the single molecule around the central perylenediimide long axis

Conformational rearrangements in and twisting of a single molecule

Single molecule spectroscopy is used to obtain detailed information on the photophysical properties of immobilized perylenediimide-based molecules, substituted in the bay positions. The fluorescence spectra recorded for numerous single molecules show a clear bimodal distribution of the peak position. Within the low energy component of the distribution, two different vibronic shapes of the emission spectrum can be seen, which can be correlated to different decay times. We show that former observation can be explained by conformational changes of the bay substituents while the latter are related to twisting of the single molecule around the central perylenediimide long axis

Upconversion Cross-Correlation Spectroscopy of a Sandwich Immunoassay

Fluorescence correlation and cross-correlation spectroscopy (FCS/FCCS) have enabled biologists to study processes of transport, binding, and enzymatic reactions in living cells. However, applying FCS and FCCS to samples such as whole blood and plasma is complicated as the fluorescence bursts of diffusing labels can be swamped by strong autofluorescence. Here we present cross-correlation spectroscopy based on two upconversion nanoparticles emitting at different wavelengths on the anti-Stokes side of a single excitation laser. This upconversion cross-correlation spectroscopy (UCCS) approach allows us to completely remove all Stokes shifted autofluorescence background in biological material such as plasma. As a proof of concept, we evaluate the applicability of UCCS to a homogeneous sandwich immunoassay for thyroid stimulating hormone measured in buffer solution and in plasma

Experimental assignment of long range magnetic communication through Pd amp; Pt metallophilic contacts

Record breaking magnetic exchange interactions have previously been reported for 3d metal dimers of the form [M Pt SAc 4 pyNO2 ]2 M Ni or Co that are linked in the solid state via metallophilic Pt amp; 8943;Pt bridges. This contrasts the terminally capped monomers [M Pt SAc 4 py 2], for which neither metallophilic bridges nor magnetic exchange interactions are found. Computational modeling has shown that the magnetic exchange interaction is facilitated by the pseudo closed shell d8 amp; 8943;d8 metallophilic interaction between the filled Pt2 5dz2 orbitals. We present here inelastic neutron scattering experiments on these complexes, wherein the dimers present an oscillatory momentum transfer dependence of the magnetic transitions. This allows for the unequivocal experimental assignment of the distance between the coupled ions, which matches exactly the coupling pathway via the metallophilic bridges. Furthermore, we have synthesized and magnetically characterized the isostructural palladium analogues. The magnetic coupling across the Pd amp; 8943;Pd bridge is found through SQUID magnetometry and FD FT THz EPR spectroscopy to be much weaker than via the Pt amp; 8943;Pt bridge. The weaker coupling is traced to the larger radial extent of the 5dz2 orbitals compared to that of the 4dz2 orbitals. The existence of a palladium metallophilic interaction is evaluated computationally from potential surface cuts along the metal stretching direction. Similar behavior is found for the Pd amp; 8943;Pd and Pt amp; 8943;Pt systems with clear minima along this coordinate and provide estimates for the force constant for this distortion. The estimated M amp; 8943;M stretching frequencies are found to match experimental observed, polarized bands in single crystal Raman spectra close to 45 cm amp; 8722;1. This substantiates the existence of energetically relevant Pd amp; 8943;Pd metallophilic interactions. The unique properties of both Pt2 and Pd2 constitutes an orthogonal reactivity, which can be utilized for steering both the direction and strength of magnetic interaction