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Plasmonic catalysis in the colloidal phase requires robust surface ligands that prevent particles from aggregation in adverse chemical environments and allow carrier flow from reagents to nanoparticles. This work describes the use of a water-soluble conjugated polymer comprising a thiophene moiety as a surface ligand for gold nanoparticles to create a hybrid system that, under the action of visible light, drives the conversion of the biorelevant NAD+ to its highly energetic reduced form NADH. A combination of advanced microscopy techniques and numerical simulations revealed that the robust metal–polymer heterojunction, rich in sulfonate functional groups, directs the interaction of electron-donor molecules with the plasmonic photocatalyst. The tight binding of polymer to the gold surface precludes the need for conventional transition-metal surface cocatalysts, which were previously shown to be essential for photocatalytic NAD+ reduction but are known to hinder the optical properties of plasmonic nanocrystals. Moreover, computational studies indicated that the coating polymer fosters a closer interaction between the sacrificial electron-donor triethanolamine and the nanoparticles, thus enhancing the reactivity., This work was supported by grant PID2019-111772RB-I00 funded by MCIN/AEI/10.13039/501100011033 and grant IT 1254-19 funded by Basque Government. The authors acknowledge the financial support of the European Commission (EUSMI, Grant 731019). S.B. is grateful to the European Research Council (ERC-CoG-2019 815128).

The interaction of several components in the strong coupling regime yielding multiple Rabi splittings opens up remarkable possibilities for studies of multimode hybridization and energy transfer, which is of considerable interest in both fundamental and applied science. Here we demonstrate that three different components, such as core−shell Au@Ag nanorods and J-aggregates of two different dyes, can be integrated into a single hybrid structure, which leads to strong collective exciton− plasmon coupling and double-mode Rabi splitting totaling 338 meV. We demonstrate strong coupling in these multicomponent plexitonic nanostructures by means of magnetic circular dichroism spectroscopy and demonstrate strong magneto-optical activity for the three hybridized states resulting from this coupling. The J-aggregates of two different nonmagnetic dyes interact with metal nanoparticles effectively, achieving magnetic properties due to the hybridization of electronic excitations in the threecomponent system., This work was supported by MINECO (Ministerio de Economiá y Competitividad), Spain, Projects FIS2016-80174-P (PLASMOQUANTA) and MAT2017-86659-R (MULTIMAGE). I.R.N. and Y.P.R. acknowledge support from the Ministry of Education and Science of the Russian Federation under Grant No. 14.Y26.31.0011 and funding from the Basque Government (Grant No. IT1164-19). This work was coordinated under the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency (Grant No. MDM-2017-0720).

Triethanolamine is a widely used model electron donor that enables a fast screening of the photocatalyst parameters in both, homogeneous and heterogeneous scenarios. We report a new role of triethanolamine in heterogeneous photoregeneration of cofactor molecules – nicotinamide adenine dinucleotide (NADH) – using state-of-the-art heterogeneous photocatalysts. In contrast to the common model involving the light-induced electrons and holes generation to reduce the substrate and oxidize triethanolamine simultaneously, we identified glycolaldehyde as a stable product of triethanolamine degradation capable of reducing NAD+. Triethanolamine, apart from playing a role of a precursor for reducing agent, maintains the alkalinity of the solution to drive the reduction. Our findings offer a fresh insight into the triethanolamine-assisted photocatalysis because glycolaldehyde as such have generally been neglected in mechanistic considerations. Moreover, a spatial and temporal decoupling of the photocatalyst from the substrate reduction reaction minimizes the product re-oxidation, thus implying a relevant feature for the real-world applications using a continuous flow setting., F. V. would like to thank ScotChem for the financial support. Y. R. would like to thank The Ministry of Education and Science of the Russian Federation (grant no. 14.Y26.31.0011).

Resonant interaction between excitonic transitions of molecules and localized electromagnetic field allows the formation of hybrid light–matter polaritonic states. This hybridization of the light and the matter states has been shown to significantly alter the intrinsic properties of molecular ensembles placed inside the optical cavity. Here, we have observed strong coupling of excitonic transition in a pair of closely located organic dye molecules demonstrating an efficient donor-to-acceptor resonance energy transfer with the mode of a tuneable open-access cavity. Analysing the dependence of the relaxation pathways between energy states in this system on the cavity detuning, we have demonstrated that predominant strong coupling of the cavity photon to the exciton transition in the donor dye molecule can lead not only to an increase in the donor–acceptor energy transfer, but also to an energy shift large enough to cause inversion between the energy states of the acceptor and the mainly donor lower polariton energy state. Furthermore, we have shown that the polariton-assisted donor–acceptor chromophores' role reversal or “carnival effect” not only changes the relative energy levels of the donor–acceptor pair, but also makes it possible to manipulate the energy flow in the systems with resonant dipole–dipole interaction and direct energy transfer from the acceptor to the mainly donor lower polariton state. Our experimental data are the first confirmation of the theoretically predicted possibility of polariton-assisted energy transfer reversal in FRET systems, thus paving the way to new avenues in FRET-imaging, remote-controlled chemistry, and all-optical switching., This study was supported by the Ministry of Education and Science of the Russian Federation (grant no. 14.Y26.31.0011). I. N. acknowledges the support from the Ministry of Higher Education, Research and Innovation of the French Republic and the University of Reims Champagne-Ardenne. The part of the work devoted to the microresonator development and adaptation was supported by the Russian Science Foundation (grant no. 21-79-30048). Y. R. acknowledges the support from the Basque Government (grant no. IT1164-19).

Strong exciton–plasmon interaction enables effective control of the photonic properties of hybrid organic–inorganic nanostructures encompassing light absorption, scattering and luminescence. Whereas the manifestations of light-matter interactions in the absorption and scattering are reasonably well understood their relation to the luminescence as well as luminescence properties themselves in strongly coupled plexcitonic hybrids is still largely underexplored especially for a system with a complex mechanism of hybridisation of states. Here we report on investigation of the interaction between localized and hybridized plasmons in gold nanostars and excitons in J-aggregates under ambient conditions. Our findings demonstrate the quality performance of the formed plexciton system with multiple hybridization channels in terms of the parameters of strong coupling, such as Rabi splitting (230 meV), coupling-strength-to-transition energy ratio (0.07), and cooperativity (2.03). The results of time-resolved experiments elucidate the observed enhanced spontaneous emission rate with regard to the Purcell effect, whose value was estimated from the extinction spectra of the strongly coupled plexciton system., Financial supports from Projects PID2019-111772RB-I00 of the Spanish MINECO and the Ministry of Science and Higher Education of the Russian Federation (Grant No. 14.Y26.31.0011) are acknowledged. Y. R. acknowledges the support from the Basque Government (grant no. IT1164-19). P.S. and I.N acknowledge support from the Russian Science Foundation (grant no. 21-79-30048) of the part of this work related to nanomaterials manufacturing and functionalisation. I.N. acknowledges support from the Université de Reims Champagne-Ardenne. A.S.-I. acknowledges the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency (Grant No. MDM-2017-0720).

Semiconductor quantum dots (QDs) are widely used in photovoltaic and optoelectronic devices due to their unique optical properties. Photoluminescence (PL) properties of QDs can be significantly improved by their electromagnetic coupling with plasmonic nanoparticles (PNPs). The excitation of resonant localized plasmon modes leads to the enhancement of the density of photon states and increase of electromagnetic field near the surface of PNPs, what boosts the acceleration of the exciton radiative decay, known as the Purcell effect. To study the dependence of the degree of acceleration of radiative decay rate (Purcell factor) on the distance between QDs and PNPs, we fabricated thin-film hybrid structures based on CdSe(core)/ZnS/CdS/ZnS(multishell) QDs and silver or gold PNPs with a controllable distance between these components. The change in the radiative decay rate of excitons was calculated from the PL intensities and lifetimes before and after the deposition of PNPs on top of the QD thin film covered by a poly(methyl methacrylate) (PMMA) spacer. For both PNP types, the PL lifetime of underlying QDs decreased, whereas the PL intensity of the latter decreased only slightly for gold PNPs and even increased for silver PNPs. This indicates the acceleration of QDs radiative decay (Purcell effect) mediated by exciton-plasmon interaction. The Purcell factor was higher for silver PNPs than that for gold PNPs, what can be explained by the better spectral overlap between the QDs PL band and silver PNPs absorbance and the absence of interband absorption in silver at the wavelength of QDs PL. The results of this study provide better understanding of the Purcell effects in hybrid materials based on QDs and PNPs.

Efficient biexciton (BX) photoluminescence (PL) from quantum dots (QDs) paves the way to the generation of entangled photons and related applications. However, the quantum yield (QY) of BX PL is much lower than that for single excitons (EX) due to efficient Auger-like recombination. In the vicinity of plasmon nanoparticles, the recombination rates of EX and BX may be affected by the Purcell effect, fluorescence quenching, and the excitation rate enhancement. Here, the effect of the plasmon resonance spectral position on the EX and BX PL is experimentally studied in two cases: when the plasmon band overlaps with the excitation wavelength and when it coincides with the QDs PL band. In the first case, the EX and BX excitation efficiencies are significantly increased but the EX QY reduced. As a result, the BX-to-EX QY ratio is higher than 1 at plasmon–exciton systems separations shorter than 40 nm. In the second case, the radiative recombination rates are enhanced by several orders of magnitude, which led to an increase in BX QY over distances of up to 90 nm. Finally, these two effects are obtained in the same hybrid structure, with the resultant increase in both excitation efficiency and QY of BX PL., They also acknowledge the financial support from theMinistry of Science and Higher Education of the Russian Federation (Grant Number: 14.Y26.31.0011) . Y.R. acknowledges the support from the Basque Government (IT1164‐19)

Hybridized plexcitonic states have unique properties which have been widely studied in recent decades in many research fields targeted at both fundamental science and innovative applications. However, to make these applications come true one needs to ensure the stabilization and preservation of electronic states and optical transitions in hybrid nanostructures, especially under the influence of external stressors, in regimes, that have not yet been comprehensively investigated. The present work shows that the nanohybrid system, composed of plasmonic nanoparticles and J-aggregates of organic molecules, displays outstanding resistance to harsh environmental stressors such as temperature, pH and strong light irradiation as well as demonstrates long-term stability and processability of the nanostructures both in weak and strong coupling regimes. These findings contribute to a deeper understanding of the physicochemical properties of plexcitonic nanoparticles and may find important implications for the development of potential applications in optoelectronics, optical imaging and chemo-bio-sensing and, in general, in the field of optical materials science., Authors acknowledge the financial support from the Ministry of Education and Science of the Russian Federation (grant no. 14.Y26.31.0011). Y. R. acknowledges the support from the Basque Government (grant no. IT1164-19). M. G. acknowledges support from the Basque Government (PIBA 2018-34), and Diputación Foral de Guipúzcoa (RED 2018, RED 2019). A. S. I. acknowledges the Maria de Maeztu Units of Excellence Programme – Grant No. MDM-2017-0720 Ministry of Science, Innovation and Universities.

International audience; Resonance interaction between a molecular transition and a confined electromagnetic field can reach the coupling regime where coherent exchange of energy between light and matter becomes reversible. In this case, two new hybrid states separated in energy are formed instead of independent eigenstates, which is known as Rabi splitting. This modification of the energy spectra of the system offers new possibilities for controlled impact on various fundamental properties of coupled matter (such as the rate of chemical reactions and the conductivity of organic semiconductors). To date, the strong coupling regime has been demonstrated in many configurations under different ambient conditions. However, there is still no comprehensive approach to determining parameters for achieving the strong coupling regime for a wide range of practical applications. In this review, a detailed analysis of various systems and corresponding conditions for reaching strong coupling is carried out and their advantages and disadvantages, as well as the prospects for application, are considered. The review also summarizes recent experiments in which the strong coupling regime has led to new interesting results, such as the possibility of collective strong coupling between X-rays and matter excitation in a periodic array of Fe isotopes, which extends the applications of quantum optics; a strong amplification of the Raman scattering signal from a coupled system, which can be used in surface-enhanced and tip-enhanced Raman spectroscopy; and more efficient second-harmonic generation from the low polaritonic state, which is promising for nonlinear optics. The results reviewed demonstrate great potential for further practical applications of strong coupling in the fields of photonics (low-threshold lasers), quantum communications (switches), and biophysics (molecular fingerprinting).

Plasmonic nanoparticles (PNPs) can significantly modify the optical properties of nearby organic molecules and thus present an attractive opportunity for sensing applications. However, the utilization of PNPs in conventional absorption, fluorescence, or Raman spectroscopy techniques is often ineffective due to strong absorption background and light scattering, particularly in the case of turbid solutions, cell suspensions, and biological tissues. Here we show that nonmagnetic organic molecules may exhibit magneto-optical response due to binding to a PNP. Specifically, we detect strong magnetic circular dichroism signal from supramolecular J-aggregates, a representative organic dye, upon binding to silver-coated gold nanorods. We explain this effect by strong coupling between the J-aggregate exciton and the nanoparticle plasmon, leading to the formation of a hybrid state in which the exciton effectively acquires magnetic properties from the plasmon. Our findings are fully corroborated by theoretical modeling and constitute a novel magnetic method for chemo- and biosensing, which (upon adequate PNP functionalization) is intrinsically insensitive to the organic background and thus offers a significant advantage over conventional spectroscopy techniques., We acknowledge financial support from Project Fis2016.80174-P (PLASMOQUANTA) from MINECO (Ministerio de Economia y Competitividad). L.L.-M. acknowledges funding from the European Research Council (ERC Advanced Grant 267867, Plasmaquo).

Studies of resonance interaction between matter and localized electromagnetic field in a cavity have recently attracted much interest because they offer the possibility of controllably modifying some of the fundamental material properties. However, despite the large number of such studies, these is no universal approach that would allow investigation of sets of different samples with wide variation of the main experimental parameters of the optical modes. In this work, the main optical parameters of a previously developed universal tunable microcavity cell, i.e., the Q factor and mode volume, as well as their dependence on the characteristics of cavity mirrors and spacing between them, are analyzed. The results obtained will significantly expand the scope of applications of resonance interaction between light and matter, including such effects as the enhancement of Raman scattering, long-range resonance nonradiative energy transfer, and modification of chemical reaction rates., This work was supported by the Ministry of Science and Higher Education of the Russian Federation,contract no. 4.Y26.31.0011.

Resonance interaction between a localized electromagnetic field and excited states in molecules paves the way to control fundamental properties of a matter. In this study, we encapsulated organic molecules with relatively low unoriented dipole moments in the polymer matrix, placed them in tunable optical microcavity and realized, for the first time, controllable modification of the broad photoluminescence (PL) emission of these molecules in strong coupling regime at room temperature. Notably, while in most previous studies it was reported that the single mode dominates in the PL signal (radiation of the so-called branch of the lower polariton), here we report on the observation of two distinct PL peaks, evolution of which has been followed as the microcavity mode is detuned from the excitonic resonance. A significant Rabi splitting estimated from the modified PL spectra was as large as 225 meV. The developed approach can be used both in fundamental research of resonant light-mater coupling and its practical applications in sensing and development of coherent spontaneous emission sources using a combination of carefully designed microcavity with a wide variety of organic molecules., Ministry of Education and Science of the Russian Federation (14.Y26.31.0011); Ministerio de Economiá y Competitividad (FIS2016.80174-P, PLASMOQUANTA).

Semiconductor quantum dots (QDs) are widely used as components of hybrid materials for development of efficient light emitters and convertors. Their unique nonlinear optical properties, such as two-photon absorption and two-photon photoluminescence from biexcitons, make them promising materials for photovoltaic and optoelectronic applications. In this study, thin-film hybrid materials based on the CdSe(core)/ZnS/CdS/ZnS(multishell) QDs have been fabricated, and the two-photon photoluminescence (PL) from the generated biexcitons have been studied. The results show that fabricated thin-film hybrid materials based on the QDs are efficient fluorophores in the one- and two-photon PL regimes for applications in optoelectronics and biosensing.

The light-matter interaction between a molecule and confined electromagnetic field is of great interest because it allows tuning the energy states and the spectral properties of the coupled matter. This effect offers a great number of applications in many areas, such as nonlinear physics, biosensing and lasing. The most widely used approach to achieve light-matter coupling is to place an ensemble of molecules inside an optical cavity. In order to maximize the effects of interaction, it is necessary to model the spectral properties of the cavity in order to find the optimal parameters for the experiments. In this study, the model for the numerical calculation of the spectral and spatial properties of electromagnetic modes of a tunable microcavity was developed and a mode analysis has been performed. The cavity transmission spectra and the electromagnetic field distribution were investigated. The results showed a good agreement with the experimental data obtained earlier.

An understanding of the mechanisms of energy transfer and conversion on the nanoscale is one of the key requirements for an implementation of highly efficient photonic nanodevices based on hybrid organic/inorganic nanomaterials. In this work we conduct steady-state and time resolved optical studies of the emission properties of an ensembles and single semiconductor quantum dots and attached organic dye molecules. We revealed that the luminescence intensity of a hybrid structure does not follow the blinking behavior of quantum dots. We also demonstrated an efficient single photon generation from single hybrid nanostructures which involves an energy transfer from donor to acceptor as main excitation source., This work was supported by the Ministry of Education and Science of the Russian Federation under grant no. 14.Y26.31.0011. Y. R. and T. H. acknowledges support from Project Fis2016.80174-P (PLASMOQUANTA) from MINECO (Ministerio de Economiá y Competitividad), Spain.

Single crystal needle-like diamonds shaped as rectangular pyramids were produced by combination of chemical vapor deposition and selective oxidation with dimensions and geometrical characteristics depending on the deposition process parameters. Photoluminescence spectra and their dependencies on wavelength of excitation radiation reveal presence of nitrogen- and silicon-vacancy color centers in the diamond crystallites. Photoluminescence spectra, intensity mapping, and fluorescence lifetime imaging microscopy indicate that silicon-vacancy centers are concentrated at the crystallites apex while nitrogen-vacancy centers are distributed over the whole crystallite. Dependence of the photoluminescence on excitation radiation intensity demonstrates saturation and allows estimation of the color centers density. The combination of structural parameters, geometry and photoluminescent characteristics are prospective for advantageous applications of these diamond crystallites in quantum information processing and optical sensing., Authors are grateful for financial support from Russian Federation President Program for young scientist: Grant# МК-9230.2016.2 (for EAO and FTT) and Grant# MK-5860.2016.2 (for KGK).

Based on analogy between quantum mechanics and the classical electrodynamics, we sorted dielectric microspheres with almost identical positions of their whispering gallery mode (WGM) resonances as photonic atoms. Such microspheres were assembled in a wide range of structures including linear chains and planar photonic molecules. We studied WGM hybridization effects in such structures using side coupling by tapered microfibers as well as finite difference time domain modeling. We demonstrated that the patterns of WGM spectral splitting are representative of the symmetry, number of constituting atoms and topology of the photonic molecules. Such splitting patterns can be viewed as “spectral signatures” of corresponding molecules. Excellent agreement was found between measured and calculated fiber-transmission spectra for different molecules.

Based on analogy between quantum mechanics and the classical electrodynamics, we sorted dielectric microspheres with almost identical positions of their whispering gallery mode (WGM) resonances as photonic atoms. Such microspheres were assembled in a wide range of structures including linear chains and planar photonic molecules. We studied WGM hybridization effects in such structures using side coupling by tapered microfibers as well as finite difference time domain modeling. We demonstrated potential sensing functionality as well as new ways of controlling WGM coupling constants in such molecules. Excellent agreement was found between measured and calculated fiber-transmission spectra for different molecules.

Microfluidic devices present the basis of modern life sciences and chemical information processing. To control the flow and to allow optical readout, a reliable sensor material that can be easily utilized for microfluidic systems is in demand. Here, we present a new optical readout system for pH sensing based on pH sensitive, photoluminescent glutathione capped cadmium telluride quantum dots that are covalently immobilized in a poly(acrylate) hydrogel. For an applicable pH sensing the generated hybrid material is integrated in a microfluidic sensor chip setup. The hybrid material not only allows in situ readout, but also possesses valve properties due to the swelling behavior of the poly(acrylate) hydrogel. In this work, the swelling property of the hybrid material is utilized in a microfluidic valve seat, where a valve opening process is demonstrated by a fluid flow change and in situ monitored by photoluminescence quenching. This discrete photoluminescence detection (ON/OFF) of the fluid flow change (OFF/ON) enables upcoming chemical information processing., MF and SL gratefully acknowledge the cluster of Excellence “Center for Advancing Electronics Dresden (CfAED) for financial and assistant support. AD thanks the Government of the Russian Federation (Grant 074-U01) through ITMO Post-Doctoral Fellowship and the European Social Fund (ESF) for financing within the project “ChemIT”.

Mixed aerogels from semiconductor and metal nanoparticles represent an outstanding hybrid material with exceptional properties due to two striking advantages: the creation of a huge quantity of semiconductor-metal interfaces combined with a highly porous three-dimensional nanostructured network. We present a versatile synthetic pathway towards hybrid aerogels built up by joint gelation of CdTe and noble metal nanoparticles (Au, Pd and bimetallic Au/Pd). A straightforward HO treatment inducing gel formation is developed as a more elegant alternative compared to the established photooxidation approach. The use of HO allows a reproducible, simple and mild gel formation which can be easily upscaled. The tremendous influence of the HO concentration on gelation mechanism and gelation kinetics is revealed by photoluminescence quantum yield (PLQY) determinations. Resulting gels are extensively characterized via transmission electron microscopy (TEM), scanning TEM (STEM), energy dispersive X-ray analysis (EDX) as well as photoluminescence (PL) spectroscopy and PL lifetime measurements. By varying the composition of the herein presented noble metal nanoparticles in a controlled fashion the range of semiconductor-metal hybrid aerogels is widened, which demonstrates the versatility and consistency of our approach. This synthetic flexibility grants access to a variety of different mixed hybrid aerogels which are of high significance for catalytic, sensing and photonic applications., Parts of TEM investigations have been carried out at the Leibniz-Institut für Polymerforschung Dresden e.V. Access to their TEM facility is gratefully acknowledged. AD thanks the Government of the Russian Federation (Grant 074-U01) through ITMO Post-Doctoral Fellowship.

Resumen del trabajo presentado a la 19th International Conference on Transparent Optical Networks (ICTON), celebrada en Girona (España) del 2 al 6 de julio de 2017., We report our recent results of investigation of the interactions between localized plasmons in gold nanorods and excitons in J-aggregates. We 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 show 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.

This work takes inspiration from chemistry where the spectral characteristics of the molecules are determined by hybridization of electronic states evolving from the individual atomic orbitals. Based on analogy between quantum mechanics and the classical electrodynamics, we sorted dielectric microspheres with almost identical positions of their whispering gallery mode (WGM) resonances. Using these microspheres as classical photonic atoms, we assembled them in a wide range of structures including linear chains and planar photonic molecules. We studied WGM hybridization effects in such structures using side coupling by tapered microfibers as well as finite difference time domain modeling. We demonstrated that the patterns of WGM spectral splitting are representative of the symmetry, number of constituting atoms and topology of the photonic molecules which in principle can be viewed as “spectral signatures” of various molecules. We also show new ways of controlling WGM coupling constants in such molecules. Excellent agreement was found between measured transmission spectra and spectral signatures of photonic molecules predicted by simulation., The authors gratefully acknowledge support from U.S. Army Research Office through Dr. J. T. Prater under Contract No. W911NF‐09‐1‐0450 and DURIP W911NF‐11‐1‐0406 and W911NF‐12‐1‐0538. This work was also supported by Center for Metamaterials, an NSF I/U CRC, Award No. 1068050. Also, this work was sponsored by the Air Force Research Laboratory (AFRL/RYD, AFRL/RXC) through the AMMTIAC contract with Alion Science and Technology and the MCF II contract with UES, Inc.

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.

Strong coupling of plasmons and excitons can form hybrid states, the so called “plexcitons”. Especially with molecular J-aggregated dye molecules strong interaction becomes observable even under ambient conditions. In our work we investigate the nature of plexcitonic states formed in gold nanorods coated with a cyanine dye by transient absorption spectroscopy. We demonstrate that plexcitons show tunable plasmonic and excitonic non-linear optical behaviour. Our experimental data can be explained on the basis of a simple Lorentz oscillator model. We find that both the quality factor and the coupling strength between plasmons and excitons can be optically manipulated on an ultrashort time scale. T. Simon, D. Melnikau, A. Sanchez-Iglesias, M. Grzelczak, L. Liz-Marzan, Y. Rakovich, J. Feldmann and A. Urban, Exploring the optical non-linearities of plasmon-exciton hybrid resonances in coupled colloidal nanostructures, submitted (2016)

The effect of induced transparency, which is related to photoinduced bleaching of photoabsorbers, is being intensely studied and has many applications in the field of sensing. Along with this classical effect, numerous studies on induced transparency in coupled plasmon–exciton systems, which is accompanied by the formation of hybrid states, have been recently published. The formation of a new coupled system results in various spectral modifications. For example, induced transparency manifests itself as a narrow dip in the absorption spectrum of a coupled system. This effect can be used in sensing, the feasibility of which is the main objective here, where a variety of materials and methods for obtaining the induced transparency are considered. Various morphologies and geometries of plasmonic nanoparticles are discussed as well as types of molecular absorbers to assess the most favorable combinations for the evolvement of induced transparency. The potential applications of the induced transparency effect in sensing and molecular diagnostics are summarized., The Ministry of Education and Science of the Russian Federation, grant no. 14.Y26.31.0011, supported this study. Support from the project Fis2016.80174-P (PLASMOQUANTA) from MINECO (Ministerio de Economiá y Competitividad), Spain, is also acknowledged.

The interaction between the excitonic J-band of J-aggregate molecules and localized plasmonic resonances supported by metallic structures can be large enough to reach the regime of strong coupling, giving rise to two hybridized modes [1, 2]. The new hybrid system is often characterized in extinction measurements, where the strong coupling results in an avoided crossing of the two modes as the detuning of the plasmonic mode with respect to the excitonic transition is changed. In principle, the photoluminescence (PL) signal should also exhibit a characteristic anti-crossing signature, but, so far, it has been challenging to identify it in experiments [2, 3].

We experimentally and theoretically investigate the interactions between localized plasmons in gold nanorods and excitons in J-aggregates under ambient conditions. Thanks to our sample preparation procedure we are able to track a clear anticrossing behavior of the hybridized modes not only in the extinction but also in the photoluminescence (PL) spectra of this hybrid system. Notably, while previous studies often found the PL signal to be dominated by a single mode (emission from so-called lower polariton branch), here we follow the evolution of the two PL peaks as the plasmon energy is detuned from the excitonic resonance. Both the extinction and PL results are in good agreement with the theoretical predictions obtained for a model that assumes two interacting modes with a ratio between the coupling strength and the plasmonic losses close to 0.4, indicative of the strong coupling regime with a significant Rabi splitting estimated to be ∼200 meV. The evolution of the PL line shape as the plasmon is detuned depends on the illumination wavelength, which we attribute to an incoherent excitation given by decay processes in either the metallic rods or the J-aggregates., We acknowledge financial support from Projects FIS2013-41184-P and MAT2013-46101-R of the Spanish Ministry of Economy and Competitiveness (MINECO) and ETORTEK project NANOGUNE’14. R.E. acknowledges funding as Fellow Gipuzkoa of the Gipuzkoako Foru Aldundia through Feder Funds of the European Union “Una manera de hacer Europa”.

We studied the chiroptical properties of colloidal solution of CdSe and CdSe/ZnS quantum dots (QDs) with a cubic lattice structure which were initially prepared without use of any chiral molecules and coated with achiral ligands. We demonstrate circular dichroism (CD) activity around first and second excitonic transition of these CdSe based nanocrystals. We consider that this chiroptical activity is caused by imbalance in racemic mixtures of QDs between the left and right handed nanoparticles, which appears as a result of the formation of various defects or incorporation of impurities into crystallographic structure during their synthesis. We demonstrate that optical activity of colloidal solution of CdSe QDs with achiral ligands weakly depends on the QDs size and number of ZnS monolayers, but does not depend on the nature of achiral ligands or polarity of the solution., Project FIS2013-41184-P of the Spanish Minsitry of Economy and Competitiveness MINECO.

We report on direct formation of J-aggregates in cyanine dye solution by injection of colloidal CdTe quantum dots. The optical properties of formed J-aggregates have been investigated by absorption and photoluminescence spectroscopy and fluorescence lifetime imaging microscopy. Quantum dots/J-aggregate system shows the enhanced absorption in visible and ultraviolet parts of the spectrum typical of quantum dots, along with the narrow emission linewidth and fast recombination rate characteristic of the J-band emitters. Our studies suggest electrostatic association between the J-aggregates and quantum dots, followed by highly efficient energy transfer. Copyright © 2012 American Scientific Publishers All rights reserved.

Physikalische Chemie/Elektrochemie, TU Dresden, Bergstr. 66b, 01062 Dresden, GermanyIn this work we report on the development of novel hybrid material with enhanced photodynamicproperties based on methylene blue and CdTe nanocrystals. Absorption spectroscopy, visible photo-luminescence spectroscopy and ”uorescence lifetime imaging of this system reveal ef“cient chargetransfer between nanocrystals and the methylene blue dye. Near infra-red photoluminescencemeasurements provide evidence for an increased ef“ciency of singlet oxygen production by themethylene blue dye. In vitro studies on the growth of HepG2 and HeLa cancerous cells were alsoperformed, they point towards an improvement in the cell kill ef“ciency for the methylene blue-semiconductor nanocrystals hybrid system.

In recent years the studies of electromagnetic modes in solid spherical microcavities have been of great interest both for their potential applications and fundamental optical properties. A system of coherently coupled microcavities may be called a “photonic molecule” and can be employed in the tight-binding device in order to manipulate photons in micrometer length scale. In this work we demonstrate the possibility of mode manipulation in systems of symmetric photonic molecules formed by placing several high-Q micro-spheres in contact. We observe photonic nanojets that reflect the symmetry of the photonic molecule, with 3 jets located at 120 degrees with respect to each other for the triangular photonic molecule. A benzene molecule-like structure consisting of a 7-microspheres cyclic photonic molecule shows a field emission pattern similar to the spatial distribution of the orbitals of the benzene molecule. We also present some results showing the coexistence of whispering gallery modes and photonic nanojets in the same structure.

International audience; The occurrence of metastases is one of the main causes of death in many cancers and themain cause of death for breast cancer patients. Micrometastases of disseminated tumour cellsand circulating tumour cells are present in more than 30% of breast cancer patients withoutany clinical or even histopathological signs of metastasis. Low abundance of these cell typesin clinical diagnostic material dictates the necessity of their enrichment prior to reliabledetection. Current micrometastases detection techniques are based on immunocytochemicaland molecular methods suffering from low efficiency of tumour cells enrichment andobserver-dependent interpretation. The use of highly fluorescent semiconductor nanocrystals,also known as ‘‘quantum dots’’ and nanocrystal-encoded microbeads tagged with a widepanel of antibodies against specific tumour markers offers unique possibilities for ultra-sensitive micrometastases detection in patients’ serum and tissues. The nanoparticle-baseddiagnostics provides an opportunity for highly sensitive parallel quantification of specificproteins in a rapid and low-cost method, thereby providing a link between the primarytumour and the micrometastases for early diagnosis.

In this review, we discuss the feasibility of laser cooling of semiconductor nanocrystal quantum dots by phonon-assisted anti-Stokes photoluminescence. Taking into account recent experimental advances, in particular, the development of semiconductor nanocrystals with very high quantum yield, we analyze in detail how the various physical processes in nanocrystals might help or hinder the cooling process. Possible experimental approaches to achieve efficient optical cooling are also discussed.

We will review recent advances in the investigation of optical modes in single three-dimensional whispering-gallery microcavities and coupled microresonators. Due to the small size and high quality factor these resonators have the potential for development of single-photon emitters, nanojets, sensors and low-threshold lasers and for fundamental studies of optical matter interactions.

The disclosure of the mechanisms of nanoparticle interaction with specific intracellular targets represents one of the key tasks in nanobiology. Unmodified luminescent semiconductor nanoparticles, or quantum dots (QDs), are capable of a strikingly rapid accumulation in the nuclei and nucleoli of living human cells, driven by processes of yet unknown nature. Here, it is hypothesized that such a strong tropism of QDs could be mediated by charge-related properties of the macromolecules presented in the nuclear compartments. As the complex microenvironment encountered by the QDs in the nuclei and nucleoli of live cells is primarily presented by proteins and other biopolymers, such as DNA and RNA, the model of human phagocytic cell line THP1, nuclear lysates, purified protein, and nucleic acid solutions is utilized to investigate the interactions of the QDs with these most abundant classes of intranuclear macromolecules. Using a combination of advanced technological approaches, including live cell confocal microscopy, fluorescent lifetime imaging (FLIM), spectroscopic methods, and zeta potential measurements, it is demonstrated that unmodified CdTe QDs preferentially bind to the positively charged core histone proteins as opposed to the DNA or RNA, resulting in a dramatic shift off the absorption band, and a red shift and decrease in the pholuminescence (PL) intensity of the QDs. FLIM imaging of the QDs demonstrates an increased formation of QD/protein aggregates in the presence of core histones, with a resulting significant reduction in the PL lifetime. FLIM technology for the first time reveals that the localization of negatively charged QDs to their ultimate nuclear and nucleolar destinations dramatically affects the QDs' photoluminescence lifetimes, and offers thereby a sensitive readout for physical interactions between QDs and their intracellular macromolecular targets. These findings strongly suggest that charge-mediated QD/histone interactions could provide the basis for QD nuclear localization downstream of intracellular transport mechanisms.

CdTe nanowire networks were assembled in standard physiological phosphate-buffered solution from individual CdTe nanocrystals on a time scale of minutes. TEM study revealed a chainlike internal structure of nanowires composed of nonfused CdTe nanocrystals. Individual wires within the network preserved the bright luminescence of CdTe nanocrystal building blocks, with remarkable changes in recombination kinetics for the entire nanowire network, along the single wires and at intercrossing and branching points as revealed by microphotoluminescence and fluorescence lifetime imaging microscopy.

International audience; We use high content cell analysis, live cell fluorescent imaging, and transmission electron microscopy approaches combined with inhibitorsof cellular transport and nuclear import to conduct a systematic study of the mechanism of interaction of nonfunctionalized quantum dots(QDs) with live human blood monocyte-derived primary macrophages and cell lines of phagocytic, epithelial, and endothelial nature. Livehuman macrophages are shown to be able to rapidly uptake and accumulate QDs in distinct cellular compartment specifically to QDs size andcharge. We show that the smallest QDs specifically target histones in cell nuclei and nucleoli by a multistep process involving endocytosis,active cytoplasmic transport, and entering the nucleus via nuclear pore complexes. Treatment of the cells with an anti-microtubule agentnocodazole precludes QDs cytoplasmic transport whereas a nuclear import inhibitor thapsigargin blocks QD import into the nucleus. Theseresults demonstrate that the nonfunctionalized QDs exploit the cell’s active transport machineries for delivery to specific intranuclear destinations.

We report on the state-of-the art synthesis and improved luminescence properties of thiol-capped CdTe nanocrystals (NCs) synthesized in water. The optimized pH (12) and molar ratio of thiol to Cd ions (1.3:1) increases the room-temperature photoluminescence quantum efficiency of as-synthesized CdTe NCs capped by thioglycolic acid (TGA) to values of 40−60%. By employing mercaptopropionic acid (MPA) as a stabilizer, we have synthesized large (up to 6.0 nm in diameter) NCs so that the spectral range of the NCs' emission currently available within this synthetic route extends from 500 to 800 nm. Sizing curve for thiol-capped CdTe NCs is provided. In contrast to CdTe NCs capped by TGA, MPA-capped CdTe NCs show up to 1 order of magnitude longer (up to 145 ns) emission decay times, which become monoexponential for larger particles. This phenomenon is explained by considering the energetics of the Te-related traps in respect to the valence-band position of CdTe NCs. The correlation between luminescence quantum ef...

Optical properties were studied of a novel microtube cavity of ∼8 μm diameter prepared by vacuum-assisted filtration of aluminosilicate xerogel using micro-channel glass matrix followed by thermal treatment. Periodic very narrow peaks of the emission spectra corresponding to orthogonally polarized whispering gallery modes were detected. The spectral position of different modes were analyzed using Lorenz-Mie theory. The mode assignment permits calculation of the spectral dependence of cavity Q values associated with observed peaks. Intensity-dependent, time-resolved stimulated emission experiments were performed on the single microtube cavity. The results show a strong decrease in emission lifetime with increasing excitation intensity, consistent with a mechanism of amplified stimulated emission.

Shedding light on cells: Quantum dot (QD)–gelatin nanocomposites, prepared by the synthesis of CdTe nanoparticles in the presence of gelatin, exhibit increased QD luminescence efficiencies. The nanocomposites penetrate the cell membrane and illuminate the cytoskeleton of macrophage cells (see image). Compared to the originals, the gelatin-modified QDs display significantly lower rates of cytotoxicity and improved biocompatibility.

The optical properties of diamond spherical-like particles, prepared by the hot-filament chemical vapor deposition technique on opal substrates, have been investigated. The particles were studied using scanning electron microscopy, micro-Raman spectroscopy and micro-photoluminescence techniques. The diamond particles, consisting of polycrystalline diamond, have a size of about 5 μm. Periodic peaks in the background of the photoluminescence spectra have been revealed. Analysis of the position of these peaks with the Lorentz–Mie theory for light scattering by single dielectric spherical particles confirms that these observed peaks can be regarded as whispering-gallery mode.

In this paper a novel technique for the production of aluminosilicate microtubes, which are shown to act as optical cylindrical microresonators, is described. The free-standing microtubes are fabricated by using vacuum-assisted wetting and filtration of silica gel through a microchannel glass matrix. The microtubes are studied using scanning electron microscopy, micro-photoluminescence spectroscopy, and fluorescence lifetime imaging confocal microscopy. In the emission spectra of the microresonators we find very narrow periodic peaks corresponding to the whispering gallery modes of two orthogonal polarizations with quality factors up to 3200. A strong enhancement in photoluminescence decay rates at high excitation power demonstrates the occurrence of amplified spontaneous emission from a single microtube. These microtubes show a large evanescent field extending many micrometers beyond the tube radius. Applications for these novel microresonators will be in the areas of microlasers and microsensors and quantum information processing.

A strategy to gate the emission efficiency of semiconductor nanocrystals in response to optical signals is proposed. Reversible modulation of the emission of CdTe nanocrystals has been studied utilizing energy transfer mechanisms in the hybrid spiropyran/CdTe system on a timescale of tens of seconds. The possibility of all-optical processing and optical control at molecular level with a nano-photonic system is demonstrated.

In this work we demonstrate the possibility to achieve efficient anti-Stokes photoluminescence emission and Raman scattering from semiconductor quantum dots deposited on spherical microcavity using excitation below the absorption edge of quantum dots. The largest spectral shift in photoluminescence spectra to shortwave region with respect to the excitation energy was found to be 380 meV, with periodic structure in optical spectra arising from the coupling between the emission from quantum dots and spherical cavity modes.

We present our recent results on the development and characterization of hybrid sytems consisting of plasmonic nanostructures and organic dye molecules in a J-aggregate state. The measured spectra exhibit a strongly suppressed signal at wavelengths which correspond to the J-aggregate band, which is indicative of strong interaction between the plasmonic and excitonic systems.