Chiral templating of self-assembling nanostructures by circularly polarized light

PMCID: PMC4387888.-- et al.The high optical and chemical activity of nanoparticles (NPs) signifies the possibility of converting the spin angular momenta of photons into structural changes in matter. Here, we demonstrate that illumination of dispersions of racemic CdTe NPs with right- (left-)handed circularly polarized light (CPL) induces the formation of right- (left-)handed twisted nanoribbons with an enantiomeric excess exceeding 30%, which is â 1/410 times higher than that of typical CPL-induced reactions. Linearly polarized light or dark conditions led instead to straight nanoribbons. CPL templating of NP assemblies is based on the enantio-selective photoactivation of chiral NPs and clusters, followed by their photooxidation and self-assembly into nanoribbons with specific helicity as a result of chirality-sensitive interactions between the NPs. The ability of NPs to retain the polarization information of incident photons should open pathways for the synthesis of chiral photonic materials and allow a better understanding of the origins of biomolecular homochirality.This material is based on work partially supported by the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award number #DE-SC0000957, and by ARO MURI W911NF-12-1-0407 ‘Coherent Effects in Hybrid Nanostructures for Lineshape Engineering of Electromagnetic Media’ (N.A.K. and S.L.). We acknowledge support from the NSF under grant ECS-0601345; CBET 0933384; CBET 0932823; and CBET 1036672. Financial support from the Robert A. Welch Foundation (C-1664) is also acknowledged (S.L.). Support from the NIH grant GM085043 (P.Z.) is gratefully acknowledged. The work of P.K. was supported by the NSF DMR grant No. 1309765 and by the ACS PRF grant No. 53062-ND6.Peer Reviewe

Fluorescence of a photosensitizer based on an indotricarbocyanine dye in photochemotherapy

We present the results for studies of the spectral luminescence properties of a symmetric indotricarbocyanine dye (PD1) in HeLa tumor cells and animal tissues in vivo during a photochemotherapy session and after the end of the session. We have established that when the dye is exposed to light in tumor tissues, changes occur in the position and half-width of the dye fluorescence spectra, while in a culture of HeLa cells its spectral characteristics are constant. Based on analysis of the effect of overlap between the absorption spectra of endogenous biomolecules and the fluorescence spectra of the dye plus comparison of the experimental data with numerical modeling results, we have concluded that the observed changes in the fluorescence spectra of PD1 in vivo are due to a change in the ratio of the different forms of hemoglobin in the tumor tissue. We have shown that the spectral characteristics of PD1, fluorescing in the near IR range, correlate with the depth of tumor tissue necrosis achieved on exposure to light. We have established that tumor tissue necrosis occurs down to a depth of 2 cm in the case of all strains studied: S-45, SM-1, and W-256, where as a result of exposure to light, we observe an increase in the half-width and a short-wavelength shift of the fluorescence spectrum of the dye PD1, and also the intensity of its fluorescence does not recover

A preliminary factor analytic investigation into the first-order factor structure of the Fifteen Factor Plus (15FQ+) on a sample of Black South African managers

The original publication is available at http://www.sajip.co.zaMoyo, S. & Theron, C. 2011. A preliminary factor analytic investigation into the first-order factor structure of the Fifteen Factor Plus (15FQ+) on a sample of Black South African managers. SA Journal of Industrial Psychology, 37(1), 1-22, doi: 10.4102/sajip.v37i1.934.Orientation: The Fifteen Factor Questionnaire Plus (15FQ+) is a prominent personality questionnaire that organisations frequently use in personnel selection in South Africa. Research purpose: The primary objective of this study was to undertake a factor analytic investigation of the first-order factor structure of the 15FQ+. Motivation for the study: The construct validity of the 15FQ+, as a measure of personality, is necessary even though it is insufficient to justify its use in personnel selection. Research design, approach and method: The researchers evaluated the fit of the measurement model, which the structure and scoring key of the 15FQ+ implies, in a quantitative study that used an ex post facto correlation design through structural equation modelling. They conducted a secondary data analysis. They selected a sample of 241 Black South African managers from a large 15FQ+ database. Main findings: The researchers found good measurement model fit. The measurement model parameter estimates were worrying. The magnitude of the estimated model parameters suggests that the items generally do not reflect the latent personality dimensions the designers intended them to with a great degree of precision. The items are reasonably noisy measures of the latent variables they represent. Practical/managerial implications: Organisations should use the 15FQ+ carefully on Black South African managers until further local research evidence becomes available. Contribution/value-add: The study is a catalyst to trigger the necessary additional research we need to establish convincingly the psychometric credentials of the 15FQ+ as a valuable assessment tool in South Africa.Publisher's versio

Influence of photon energy on the efficiency of photochemotherapy

It is found that when indotricarbocyanine dye in HeLa cells is exposed to photons with different energies the efficiency of cell damage is wavelength independent provided the photosensitizer absorbs the same number of photons per unit time. In vivo animal experiments with two strains of tumor show that when the wavelength of the irradiating light is increased (668, 740, and 780 nm) and the number of photons absorbed per unit time per unit volume of the tumors is held constant, the damage depth increases by a factor of 1.5 and 3, respectively. The observed changes are related both to differences in the in vivo tissue optical transmission with increasing wavelength and an increased local concentration of oxygen owing to photodissociation of oxy-hemoglobin

Resonance energy transfer in self-organized organic/inorganic dendrite structures

Hybrid materials formed by semiconductor quantum dots and J-aggregates of cyanine dyes provide a unique combination of enhanced absorption in inorganic constituents with large oscillator strength and extremely narrow exciton bands of the organic component. The optical properties of dendrite structures with fractal dimension 1.7–1.8, formed from J-aggregates integrated with CdTe quantum dots (QDs), have been investigated by photoluminescence spectroscopy and fluorescence lifetime imaging microscopy. Our results demonstrate that (i)J-aggregates are coupled to QDs by F¨orster-type resonant energy transfer and (ii) there are energy fluxes from the periphery to the centre of the structure, where the QD density is higher than in the periphery of the dendrite. Such an anisotropic energy transport can be only observed when dendrites are formed from QDs integrated with J-aggregates. These QD/ J-aggregate hybrid systems can have applications in light harvesting systems and optical sensors with extended absorption spectra.Fundação para a Ciência e a Tecnologia (FCT

Influence of photon energy on the efficiency of photochemotherapy

It is found that when indotricarbocyanine dye in HeLa cells is exposed to photons with different energies the efficiency of cell damage is wavelength independent provided the photosensitizer absorbs the same number of photons per unit time. In vivo animal experiments with two strains of tumor show that when the wavelength of the irradiating light is increased (668, 740, and 780 nm) and the number of photons absorbed per unit time per unit volume of the tumors is held constant, the damage depth increases by a factor of 1.5 and 3, respectively. The observed changes are related both to differences in the in vivo tissue optical transmission with increasing wavelength and an increased local concentration of oxygen owing to photodissociation of oxy-hemoglobin

Effect of surface plasmon resonance in TiO2/Au thin films on the fluorescence of self-assembled CdTe QDs structure

The exceptional properties of localised surface plasmons (LSPs), such as local field enhancement and confinement effects, resonant behavior, make them ideal candidates to control the emission of luminescent nanoparticles. In the present work, we investigated the LSP effect on the steady-state and time-resolved emission properties of quantum dots (QDs) by organizing the dots into self-assembled dendrite structures deposited on plasmonic nanostructures. Self-assembled structures consisting of water-soluble CdTe mono-size QDs, were developed on the surface of co-sputtered TiO2 thin films doped with Au nanoparticles (NPs) annealed at different temperatures. Their steady-state fluorescence properties were probed by scanning the spatially resolved emission spectra and the energy transfer processes were investigated by the fluorescence lifetime imaging (FLIM) microscopy. Our results indicate that a resonant coupling between excitons confined in QDs and LSPs in Au NPs located beneath the self-assembled structure indeed takes place and results in (i) a shift of the ground state luminescence towards higher energies and onset of emission from excited states in QDs, and (ii) a decrease of the ground state exciton lifetime (fluorescence quenching).Financial support from the European Science Foundation (ESF) through PLASMON-BIONANOSENSE programme and Portuguese Foundation for Science and Technology (FCT) and FEDER through Projects PTDC-FIS-113199-2009 and PEst-C/FIS/UI0607/2013 are gratefully acknowledged. DM, DS and YR acknowledge support from Project FIS2013-41184-P of the Spanish Ministry of Economy and Competitiveness MINECO

Strong coupling effects in hybrid plexitonic systems

Trabajo presentado a la 3rd International Conference on Applications of Optics and Photonics, celebrado en Faro (Portugal) del 8 al 12 de mayo de 2017.We investigated the interactions between localized plasmons in gold nanorods and excitons in J-aggregates and were able to track an anticrossing behavior of the hybridized modes both in the extinction and in the photoluminescence spectra of this hybrid system. We identified the nonlinear optical behavior of this system by transient absorption spectroscopy. Finally using magnetic circular dichroism spectroscopy we showed that nonmagnetic organic molecules exhibit magneto-optical response due to binding to a plasmonic nanoparticles. In our experiments we also studied the effect of detuning as well as the effect of off- and on resonance excitation on the hybrid states.We acknowledge financial support from Project Fis2016.80174-P (PLASMOQUANTA) from MINECO (Ministerio de Economía y Competitividad). L.L.-M. acknowledges funding from the European Research Council (ERC Advanced Grant 267867, Plasmaquo). This study was supported by the Ministry of Education and Science of the Russian Federation, grant no. 14.Y26.31.0011.Peer Reviewe

Strong plasmon-exciton coupling in a hybrid system of gold nanostars and J-aggregates

This is an Open Access article distributed under the terms of the Creative Commons Attribution License.Hybrid materials formed by plasmonic nanostructures and J-aggregates provide a unique combination of highly localized and enhanced electromagnetic field in metal constituent with large oscillator strength and extremely narrow exciton band of the organic component. The coherent coupling of localized plasmons of the multispiked gold nanoparticles (nanostars) and excitons of JC1 dye J-aggregates results in a Rabi splitting reaching 260 meV. Importantly, broad absorption features of nanostars extending over a visible and near-infrared spectral range allowed us to demonstrate double Rabi splitting resulting from the simultaneous coherent coupling between plasmons of the nanostars and excitons of J-aggregates of two different cyanine dyes.This work was supported by the ETORTEK 2011–2013 project ‘nanoIKER’ from the Department of Industry of the Basque Government and by the Visiting Fellowship program of Ikerbasque Foundation.Peer Reviewe