Boris Chornik

Gold Nanoparticles Interacting with β-Cyclodextrin–Phenylethylamine Inclusion Complex: A Ternary System for Photothermal Drug Release

We report the synthesis of a 1:1 β-cyclodextrin-phenylethylamine (βCD-PhEA) inclusion complex (IC) and the adhesion of gold nanoparticles (AuNPs) onto microcrystals of this complex, which forms a ternary system. The formation of the IC was confirmed by powder X-ray diffraction and NMR analyses ((1)H and ROESY). The stability constant of the IC (760 M(-1)) was determined using the phase solubility method. The adhesion of AuNPs was obtained using the magnetron sputtering technique, and the presence of AuNPs was confirmed using UV-vis spectroscopy (surface plasmon resonance effect), which showed an absorbance at 533 nm. The powder X-ray diffractograms of βCD-PhEA were similar to those of the crystals decorated with AuNPs. A comparison of the one- and two-dimensional NMR spectra of the IC with and without AuNPs suggests partial displacement of the guest to the outside of the βCD due to attraction toward AuNPs, a characteristic tropism effect. The size, morphology, and distribution of the AuNPs were analyzed using TEM and SEM. The average size of the AuNPs was 14 nm. Changes in the IR and Raman spectra were attributed to the formation of the complex and to the specific interactions of this group with the AuNPs. Laser irradiation assays show that the ternary system βCD-PhEA-AuNPs in solution enables the release of the guest.

Modification of silicon surface with redox molecules derived from ferrocene

This study presents a new method to bind active redox molecules derived of ferrocene to the surface of single crystal silicon. The procedure consists in the reaction of hydrogenated silicon with allyl bromide activated with white light and its subsequent reaction with monolithio ferrocene in order to create a covalent union between the redox molecule and the semiconductor surface. The layers formed are electrochemically active and present a quasireversible electrochemical process which is attributed to the ferrocene molecules which are bound to the silicon surface. X-ray photoelectron spectroscopy (XPS) analysis confirms the presence of ferrocene molecules on the silicon surface.

γ-Cyclodextrin/alkylthiol inclusion compounds crystals as substrates for the formation and immobilization of gold nanoparticles produced by magnetron sputtering

In this work, we report the nanodecoration of microcrystals of inclusion compound (IC) of γ-cyclodextrin (γ-CD) that contain octanethiol, decanethiol and dodecanethiol. Crystals of these ICs provide a suitable environment for nucleation, growth and immobilization of gold nanoparticles that were obtained by the magnetron sputtering technique. The use of γ-CD IC substrates with a specific surface morphology (i.e., the functional group of the guest molecule faces outward preferentially from a crystal plane) is an efficient method for the preparation of AuNPs with low size dispersion, which is due to the high affinity between the functional group of the surfactant alkylthiol guest with the metal nanoparticles.

Evidence of the Disassembly of α-Cyclodextrin-octylamine Inclusion Compounds Conjugated to Gold Nanoparticles via Thermal and Photothermal Effects

Cyclodextrin (CD) molecules form inclusion compounds (ICs), generating dimers that are capable of encapsulating molecules derived from long-chain hydrocarbons. The aim of this study is to evaluate the structural changes experienced by ICs in solution with increasing temperatures. For this, a nuclear magnetic resonance (1H-NMR) titration was performed to determinate the stoichiometric α-cyclodextrin (α-CD):octylamine (OA) 2:1 and binding constant (k = 2.16 M−2) of ICs. Solution samples of α-CD-OA ICs conjugated with gold nanoparticles (AuNPs) were prepared, and 1H-NMR spectra at different temperatures were recorded. Comparatively, 1H-NMR spectra of the sample irradiated with a laser with tunable wavelengths, with plasmons of conjugated AuNPs, were recorded. In this work, we present evidence of the disassembly of ICs conjugated with AuNPs. Thermal studies demonstrated that, at 114 °C, there are reversible rearrangements of the host and guests in the ICs in a solid state. Migration movements of the guest molecules from the CD cavity were monitored via temperature-dependent 1H-NMR, and were verified comparing the chemical shifts of octylamine dissolved in deuterated dimethylsulfoxide (DMSO-d6) with the OA molecule included in α-CD dissolved in the same solvent. It was observed that, at 117 °C, OA exited the α-CD cavity. CD IC dimer disassembly was also observed when the sample was irradiated with green laser light.

Cyclodextrin inclusion compound crystals for growth of Cu–Au core–shell nanoparticles

The preparation and structural elucidation of the 2α-cyclodextrin/decylamine inclusion compound (IC) by proton nuclear magnetic resonance, rotating frame overhauser effect spectroscopy and powder X-ray diffraction have been achieved. The IC microcrystals were used as a support for the preparation of Au–Cu core–shell nanoparticles by the sputtering method. The coating of copper nanoparticles with gold was verified through anodic stripping voltammetry. The presence of metallic copper and the absence of copper oxides were determined by X-ray photoelectron spectroscopy. These results show that the formation of core–shell Cu–Au by sputtering is an effective approach to prevent the oxidation of Cu particles, leading to potential applications in nanoelectronics.Graphical Abstract