Supramolecular assemblies of semiconductor quantum dots and a bis(bipyridinium) derivative : luminescence quenching and aggregation phenomena

We have synthesized CdSe and CdSe–ZnS core–shell luminescent nanocrystal quantum dots and studied their interaction with a ditopic bis(bipyridinium) compound in solution. The latter strongly quenches the luminescence of the quantum dots by a static mechanism, indicating that the nanocrystal and molecular components undergo association in the ground state. Photoexcitation of these inorganic–organic hybrids causes an electron-transfer process from the conduction band of the nanocrystal to the LUMO of the molecule. The ability of the bipyridinium-type species to trigger association of the quantum dots is evidenced by spectrofluorimetric titrations and DLS measurements in solution, and confirmed by TEM experiments on surfaces. The quantum dot–molecule complexes can be disassembled in solution by addition of a calixarene host capable of encapsulating the bipyridinium units of the molecular connector. Our results demonstrate that supramolecular chemistry offers convenient ways to control the aggregation of semiconductor nanocrystals, a crucial task for the generation of nanostructured arrays with well defined properties

Supramolecular assemblies of semiconductor quantum dots and a bis(bipyridinium) derivative: luminescence quenching and aggregation phenomena

We have synthesized CdSe and CdSe\u2013ZnS core\u2013shell luminescent nanocrystal quantum dots and studied their interaction with a ditopic bis(bipyridinium) compound in solution. The latter strongly quenches the luminescence of the quantum dots by a static mechanism, indicating that the nanocrystal and molecular components undergo association in the ground state. Photoexcitation of these inorganic\u2013organic hybrids causes an electron-transfer process from the conduction band of the nanocrystal to the LUMO of the molecule. The ability of the bipyridinium-type species to trigger association of the quantum dots is evidenced by spectrofluorimetric titrations and DLS measurements in solution, and confirmed by TEM experiments on surfaces. The quantum dot\u2013molecule complexes can be disassembled in solution by addition of a calixarene host capable of encapsulating the bipyridinium units of the molecular connector. Our results demonstrate that supramolecular chemistry offers convenient ways to control the aggregation of semiconductor nanocrystals, a crucial task for the generation of nanostructured arrays with well defined properties

An Efficient Method for the Surface Functionalization of Luminescent Quantum Dots with Lipoic Acid Based Ligands

We describe herein an operationally advantageous general methodology for efficiently activating lipoic acid based compounds, a family of popular surface ligands for semiconductor nanocrystals, through the use of a borohydride exchange resin, and the use of the activated species to replace the native surface ligands of quantum dots. The procedure enabled phase transfer of the nanocrystals between polar and aqueous media and, if unsubstituted lipoic acid was used, a facile adjustment of their solubility in a wide range of solvents with varying polarity (from hexane to water). We show that the protocol is applicable to different types of nanocrystals and a variety of lipoic acid based ligands, and that the resulting quantum dots maintain their optical properties, in particular, an intense luminescence, and long-term colloidal stability

An efficient method for the surface functionalization of luminescent quantum dots with lipoic acid-based ligands

We describe an operationally advantageous general methodology to efficiently activate lipoic acid-based compounds - a family of popular surface ligands for semiconductor nanocrystals - by the use of a borohydride exchange resin, and the use of the activated species to replace the native surface ligands of quantum dots. The procedure enables the phase transfer of the nanocrystals between polar and aqueous media and, if unsubstituted lipoic acid is used, a facile adjustment of their solubility in a wide range of solvents with varying polarity (from hexane to water). We show that the protocol is applicable to different types of nanocrystals and a variety of lipoic acid-based ligands, and that the resulting quantum dots maintain their optical properties - in particular, an intense luminescence - and long term colloidal stability

Synthesis and properties of ZnTe and ZnTe/ZnS core/shell semiconductor nanocrystals

Nanocrystals obtained by growing a protecting ZnS shell onto a photoactive ZnTe core afford nanocrystals that can represent alternatives to cadmium-based quantum dots

Two-stage directed self-assembly of a cyclic [3]catenane.

Interlocked molecules possess properties and functions that depend upon their intricate connectivity. In addition to the topologically trivial rotaxanes, whose structures may be captured by a planar graph, the topologically non-trivial knots and catenanes represent some of chemistry's most challenging synthetic targets because of the three-dimensional assembly necessary for their construction. Here we report the synthesis of a cyclic [3]catenane, which consists of three mutually interpenetrating rings, via an unusual synthetic route. Five distinct building blocks self-assemble into a heteroleptic triangular framework composed of two joined Fe(II)3L3 circular helicates. Subcomponent exchange then enables specific points in the framework to be linked together to generate the cyclic [3]catenane product. Our method represents an advance both in the intricacy of the metal-templated self-assembly procedure and in the use of selective imine exchange to generate a topologically complex product.This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC) and a Marie Curie fellowship for J.J.H. (ITN-2010–264645). The authors thank the Diamond Light Source (UK) for synchrotron beamtime on I19 (MT7984 and MT8464).This is the author accepted manuscript. The final version is available from NPG via http://dx.doi.org/10.1038/nchem.220

Exploiting the mechanical bond for molecular recognition and sensing of charged species

The unique properties of the mechanical bond have been increasingly used for the purpose of molecular recognition. The recent progress in the development of cation and anion template strategies for the construction of mechanically interlocked molecules (MIMs) have resulted in a variety of ion binding catenane and rotaxane host structures. The appropriate integration of reporting redox- and photo-active centres into their structural frameworks can result in prototype molecular sensors for targeting charged species and molecular switches for potential nanotechnological applications. This review presents progress in the field of MIM hosts for ion recognition and sensing since 2014, focusing on the synthetic approaches employed and mechanisms of host–guest binding and detection

Appearance of dark neurons following anodal polarization in the rat brain.

An anodal direct current of 3.0 microA or 30.0 microA was unilaterally applied for 30 min or 3 h to the surface of the sensorimotor cortex of rats, and the effects of polarization on the morphology of brain cells were examined by light microscopy. After five repeated anodal polarization trials, dark neurons appeared mainly in the polarized neocortex regardless of the intensity and duration of the polarizing currents. Such dark neurons were scarce in the control animals or the animals receiving only one trial of polarization. The dark neurons were most abundant in the second to fourth layers of the ipsilateral superior-lateral convexity of the frontal cortex, but a few were present in the contralateral cortex. The dark neurons began to appear 24 h after the last polarization; thereafter almost all of these neurons gradually reverted to their normal morphological profiles through a transitory state within 1 month of the last trial of repeated polarization. No morphological changes were apparent in any of the brain structures other than the cerebral cortex. These findings indicate that repeated anodal polarization has reversible morphological effects on the cortical neurons, suggesting that the appearance of dark neurons after anodal polarization is an important index for evaluation of cortical plastic change induced by polarization.</p

Synthesis and photophysical investigation of novel supramolecular lanthanide luminescent architectures

THESIS 9172This thesis is entitled "Synthesis and photophysical investigations of novel supramolecular architectures" and is composed of five chapters. In the first chapter the photopysical and chemical properties of the lanthanide ions was described and this was followed by a discussion on the potential different methods in order to build highy geometric lanthanide complexes, using various approaches such as the use of macrocyclic ligands, podand and lanthanide directed formation of self-assemblies, which as been most particularly described