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      Laser-induced transformation of supramolecular complexes: approach to controlled formation of hybrid multi-yolk-shell Au-Ag @a-C:H nanostructures

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          Abstract

          In the present work an efficient approach of the controlled formation of hybrid Au–Ag–C nanostructures based on laser-induced transformation of organometallic supramolecular cluster compound is suggested. Herein the one-step process of the laser-induced synthesis of hybrid multi-yolk-shell Au-Ag@a-C:H nanoparticles which are bimetallic gold-silver subnanoclusters dispersed in nanospheres of amorphous hydrogenated a-C:H carbon is reported in details. It has been demonstrated that variation of the experimental parameters such as type of the organometallic precursor, solvent, deposition geometry and duration of laser irradiation allows directed control of nanoparticles’ dimension and morphology. The mechanism of Au-Ag@a-C:H nanoparticles formation is suggested: the photo-excitation of the precursor molecule through metal-to-ligand charge transfer followed by rupture of metallophilic bonds, transformation of the cluster core including red-ox intramolecular reaction and aggregation of heterometallic species that results in the hybrid metal/carbon nanoparticles with multi-yolk-shell architecture formation. It has been found that the nanoparticles obtained can be efficiently used for the Surface-Enhanced Raman Spectroscopy label-free detection of human serum albumin in low concentration solution.

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          Absorption properties of metal-semiconductor hybrid nanoparticles.

          The optical response of hybrid metal-semiconductor nanoparticles exhibits different behaviors due to the proximity between the disparate materials. For some hybrid systems, such as CdS-Au matchstick-shaped hybrids, the particles essentially retain the optical properties of their original components, with minor changes. Other systems, such as CdSe-Au dumbbell-shaped nanoparticles, exhibit significant change in the optical properties due to strong coupling between the two materials. Here, we study the absorption of these hybrids by comparing experimental results with simulations using the discrete dipole approximation method (DDA) employing dielectric functions of the bare components as inputs. For CdS-Au nanoparticles, the DDA simulation provides insights on the gold tip shape and its interface with the semiconductor, information that is difficult to acquire by experimental means alone. Furthermore, the qualitative agreement between DDA simulations and experimental data for CdS-Au implies that most effects influencing the absorption of this hybrid system are well described by local dielectric functions obtained separately for bare gold and CdS nanoparticles. For dumbbell shaped CdSe-Au, we find a shortcoming of the electrodynamic model, as it does not predict the "washing out" of the optical features of the semiconductor and the metal observed experimentally. The difference between experiment and theory is ascribed to strong interaction of the metal and semiconductor excitations, which spectrally overlap in the CdSe case. The present study exemplifies the employment of theoretical approaches used to describe the optical properties of semiconductors and metal nanoparticles, to achieve better understanding of the behavior of metal-semiconductor hybrid nanoparticles.
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            Photochemical incorporation of silver quantum dots in monodisperse silica colloids for photonic crystal applications.

            We developed a novel method to fabricate nanocomposite monodisperse SiO2 spheres (approximately 100 nm) containing homogeneously dispersed Ag quantum dots (approximately 2 to 5 nm). The inclusion morphology is controlled through the timing of the photochemical reduction of silver ions during hydrolysis of tetraethoxysilane in a microemulsion. Depending on the timing, Ag quantum dots can be directed to different annuli within the SiO2 spheres, as well as onto the SiO2 sphere surfaces. The embedded Ag quantum dots show a plasmon resonance absorption band at 438 nm. These Ag@SiO2 particles have significant surface charge and readily self-assemble into crystalline colloidal array (CCA) photonic crystals which Bragg-diffract light in the visible region. The magnitude of the plasmon resonance absorption depends on the CCA Bragg diffraction condition. The negative dielectric constant of the silver nanoparticles may be decreasing the silica-silver nanodot composite refractive index below that of the water medium. We may be observing an analogue of the Borrmann effect previously observed in X-ray scattering, where the incident and diffracted electric field standing wave becomes localized in regions of small CCA crystal absorption.
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              Gold nanoparticles as a substrate in bio-analytical near-infrared surface-enhanced Raman spectroscopy† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4an01899k Click here for additional data file.

              “Large” nanoparticles potentially are a good starting point in order to derive informative NIR/IR SERS analysis of biological samples.
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                Author and article information

                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group
                2045-2322
                08 July 2015
                2015
                : 5
                : 12027
                Affiliations
                [1 ]Institute of Chemistry, St. Petersburg State University , Universitetskii pr. 26, St. Petersburg, 198504, Russia
                [2 ]Center for optical and laser materials research, Research park, St. Petersburg State University , Ulianovskaya St. 5, St. Petersburg, 198504, Russia
                [3 ]Interdisciplinary Resource Center for Nanotechnology, St. Petersburg State University , Ulianovskaya St. 1, St. Petersburg, 198504, Russia
                [4 ]University of Eastern Finland , Joensuu, 80101, Finland
                [5 ]Institut für Festkörperphysik, Technische Universität Dresden , D-01062 Dresden, Germany
                Author notes
                Article
                srep12027
                10.1038/srep12027
                4495562
                26153347
                fa970dd9-0915-4b06-a42c-1c5f74f12c27
                Copyright © 2015, Macmillan Publishers Limited

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 10 April 2015
                : 11 June 2015
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