Matteo Amelia

A Simple Unimolecular Multiplexer/Demultiplexer

Here we show that the reversible acid/base switching of the absorption and photoluminescence properties of a fluorophore as simple as 8-methoxyquinoline in solution can form the basis for molecular 2:1 multiplexing and 1:2 demultiplexing with a clear-cut digital response.

Probing Donor−Acceptor Interactions and Co-Conformational Changes in Redox Active Desymmetrized [2]Catenanes

We describe the synthesis and characterization of a series of desymmetrized donor-acceptor [2]catenanes where different donor and acceptor units are assembled within a confined catenated geometry. Remarkable translational selectivity is maintained in all cases, including two fully desymmetrized [2]catenanes where both donors and acceptors are different, as revealed by X-ray crystallography in the solid state, and by (1)H NMR spectroscopy and electrochemistry in solution. In all desymmetrized [2]catenanes the co-conformation is dominated by the strongest donor and acceptor pairs, whose charge-transfer interactions also determine the visible absorption properties. Voltammetric and spectroelectrochemical experiments show that the catenanes can be reversibly switched among as many as seven states, characterized by distinct electronic and optical properties, by electrochemical stimulation in a relatively narrow and easily accessible potential window. Moreover in some of these compounds the oxidation of the electron donor units or the reduction of the electron acceptor ones causes the circumrotation of one molecular ring with respect to the other. These features make these compounds appealing for the development of molecular electronic devices and mechanical machines.

Sensing Proteins with Luminescent Silica Nanoparticles

Nanometer sized silica nanoparticles (SiO2-NP) were prepared in water and loaded with two organic compounds, namely perylene and 1,6-diphenyl-1,3,5-hexatriene, which have well-defined and known fluorescence properties. The size of void and dye-doped SiO2-NP were determined by both transmission electron microscopy and atomic force microscopy, which allowed determining the loading effects on the particle size and morphology. Differently loaded nanoparticles were characterized by both steady-state and time-resolved spectrofluorimetric techniques. The spectroscopic characterization allowed in the first place to establish where the dye molecules are localized within the particles and, later, to evaluate the sensing capability of the hybrid materials with respect to proteins. In particular, dye molecules resulted to have a bimodal distribution on the particle template, specifically (i) at the particle/water interphase and (ii) in close contact with the silica surface (in the inner particle). To prove the ability of the as-prepared and characterized particles to interact with proteins, BSA and RNA-si were used as models; the particle fluorescence was used as a sensitive tool to monitor the occurrence of such interactions. In all cases, proteins interact very efficiently with the SiO2-NP mainly through static interactions likely determined by electrostatic forces. A quantitative analysis of the steady-state fluorescence quenching experiments allowed to estimate the interaction radius, which is a useful parameter to sense and to discriminate proteins.

Structural and Size Effects on the Spectroscopic and Redox Properties of CdSe Nanocrystals in Solution: The Role of Defect States

Two series of CdSe quantum dots (QDs) with different diameters are prepared, according to frequently used protocols of the same synthetic procedure. For each sample the photophysical properties and the potentials for the first reduction and oxidation processes in organic solution are determined. The band gap obtained from electrochemical experiments is compared with that determined from the absorption and luminescence spectra. While the optical band gap decreases upon increasing the nanocrystal diameter, as expected on the basis of quantum confinement, the redox potentials and the electrochemical band gap are not monotonously related to the QD size. For both series, the smallest and largest QDs are both easier to oxidize and reduce than mid-sized QDs. In fact, the latter samples exhibit very broad voltammetric profiles, which suggests that the heterogeneous electron-transfer processes from/to the electrode are kinetically hindered. Conversely, the electrochemical band gap for the smallest and largest particles of each series is somewhat smaller than the optical band gap. These results indicate that, while the optical band gap depends on the actual electron-hole recombination within the nanocrystal, and therefore follows the size dependence expected from the particle-in-a-box model, the electrochemical processes of these QDs are strongly affected by other factors, such as the presence of surface defects. The investigations suggest that the influence of these defects on the potential values is more important for the smallest and largest QDs of each series, as confirmed by the respective luminescence bands and quantum yields. An interpretation for the size-dependent evolution of the surface defects in these nanocrystals is proposed based on the mechanism of their formation and growth.

Luminescence quenching in supramolecular assemblies of quantum dots and bipyridinium dications

We have investigated the ability of two bipyridinium dications, with either octyl or decyl groups on their nitrogen atoms, to quench the luminescence of CdSe–ZnS core–shell quantum dots coated by either tri-n-octylphosphine oxide or a tris(phenylureido)calix[6]arene. Our studies demonstrate that both bipyridinium dications adsorb on the surface of the quantum dots with association constants ranging from 104 to 107 M−1 and quench the luminescence of the inorganic nanoparticles with rate constants ranging from 108 to 109 s−1. The association constants of these supramolecular assemblies vary significantly with the counterions of the bipyridinium dications and the ligands on the nanoparticle surface. Their quenching rate constants vary with the length of the alkyl chains appended to the bipyridinium core and, once again, the ligands on the nanoparticle surface. Furthermore, our studies show that the addition of a calix[6]arene able to compete with the quantum dots for the bipyridinium quenchers restores the original luminescence intensity of the nanoparticles. Indeed, the supramolecular association of the calix[6]arene with the bipyridinium dication removes the quencher from the nanoparticle surface and, hence, is transduced into a luminescent enhancement.

Redox properties of CdSe and CdSe-ZnS quantum dots in solution

Semiconductor quantum dots (QDs) are inorganic nanoparticles which, because of their unique size-dependent electronic properties, are of high potential interest for the construction of functional nanodevices. Photoinduced electron transfer is a versatile mechanism used to implement light-induced functionalities in multicomponent (supra)molecular assemblies. Indeed, QDs can be employed as active components in new generations of these systems. The rational design of the latter, however, requires prior knowledge of the photo-physical properties and redox potentials of the nanocrystals. Here we discuss the results of recent systematic electrochemical investigations aimed at understanding the structural factors that regulate the redox properties of CdSe core and CdSe–ZnS core–shell QDs.

Photophysical Properties of Quinolizinium Salts and Their Interactions with DNA in Aqueous Solution

The photophysical properties of three quinolizinium salts (naphto[2,1-b]quinolizinium bromide (Q2), naphto[1,2-b]quinolizinium bromide (Q3), and indolo[2,3-b]quinolizinium tetrafluoroborate (HI)) in fluid media and their interactions with DNA were investigated by steady-state and by nanosecond and femtosecond time-resolved techniques. The main decay pathways of the excited singlet state S(1), fluorescence, intersystem crossing, and internal conversion, were characterized in terms of quantum yields and rate constants. The lowest triplet state of the quinolizinium salts is able to sensitize singlet oxygen in rather high efficiency (phi(Delta) = 0.4 to 0.5 in MeCN). The complexes between quinolizinium salts and DNA formed in the ground state were characterized in terms of lifetimes and decay channels to give more details of the mechanism of photoinduced DNA strand break.

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

We report the synthesis of spherical ZnTe nanocrystals and the successive coating with a ZnS shell to afford core/shell quantum dots. These nanocrystals can represent alternatives to cadmium-based quantum dots but their preparation and properties are challenging and relatively unexplored. The effect of various synthetic parameters on the reaction outcome was investigated, and the resulting nanocrystals were characterized by TEM, EDX, XPS, and spectroscopic measurements. The optical data indicate that these core/shell quantum dots belong to type I, i.e., both the electron and the hole are confined within the ZnTe core. Both the ZnTe core and ZnTe/ZnS core/shell quantum dot samples absorb in the visible region and are not luminescent. The ZnS shell preserves the optical properties of the core and improves the chemical and photochemical stability of the nanoparticles in air equilibrated solution, whereas they appear to be quite fragile in the solid state. XPS results have evidenced the distinct nature of core and core/shell QDs, confirming the formation of QDs with shells of different thicknesses and their evolution due to oxidation upon air exposure. Anodic photocurrent generation was observed when an ITO electrode functionalized with ZnTe/ZnS nanocrystals was irradiated in the visible region in a photoelectrochemical cell, indicating that the quantum dots perform spectral sensitization of the electron injection into the ITO electrode. Conversely, cathodic photocurrent generation was not observed; hence, the QD-modified electrode performs electrical rectification under a photon energy input.

Luminescence quenching in self-assembled adducts of [Ru(dpp)3]2+ complexes and CdTe nanocrystals

We have investigated chloroform solutions containing tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) and CdTe nanocrystal quantum dots (5.6 nm diameter). The electronic levels of these two components are such that the Ru complex can act as an energy donor towards the quantum dot, which can thus behave as an energy acceptor. Steady-state and time-resolved spectroscopic experiments indicate that the Ru complexes and the CdTe nanocrystals self-assemble to give stable 1 : 1 adducts, in which the luminescence of the former units is strongly quenched. Such a quenching can be ascribed to either energy transfer to the CdTe quantum dot, or to electron transfer from the CdTe valence band to the excited Ru complex. However, no supporting evidence for the occurrence of photoinduced energy transfer in the adduct could be found. The CdTe luminescence is also slightly quenched in the presence of the ruthenium complex. The strong association of the metal complexes with the nanocrystals suggests that self-assembly strategies may be effectively employed to achieve surface functionalization of semiconductor quantum dots with molecular units.

Effect of protons on CdSe and CdSe-ZnS nanocrystals in organic solution.

Core and core-shell quantum dots are covered with a layer of organic ligands which prevents aggregation and eliminates surface defects, thus enhancing the photophysical properties and stability of the material. These ligands are usually Lewis bases and can therefore be affected by the presence of acid in the surrounding environment. We synthesized core CdSe and core-shell CdSe-ZnS quantum dots with various shell thicknesses and different organic ligands, and we investigated the effect of acid and base on their photophysical properties. In dilute CHCl3 solution, the organic ligands can be protonated upon addition of acid and detached from the surface of the nanoparticles. As a consequence, the nanoparticles aggregate and their luminescence is quenched. Aggregated particles can be partly disgregated and the luminescence restored by deprotonation of the free ligands with a base. Since the presence of organic ligands on the surface is an essential characteristic of quantum dots, these effects should be taken into consideration when designing quantum dot-based sensors.