Dicopper Double-Strand Helicates Held Together by Additional π–π Interactions

The bis-bidentate ligand, obtained from Schiff base condensation of <i>RR</i>-1,2-cyclohexanediamine and 8-naphthylmethoxyquinoline-2-carbaldehyde (<b>L–L</b>), forms with [Cu^I(MeCN)₄]­ClO₄ a double strand helicate complex, made especially stable by the presence of four definite interstrand π–π interactions involving a quinoline subunit and a naphthylmethoxy substituent of the two strands. The [Cu^I₂(<b>L–L</b>)₂]²⁺ complex, which does not decompose even on excess addition of either <b>L–L</b> or Cu^I, undergoes a two electron oxidation in MeCN, through two one-electron fully reversible steps, separated by 260 mV, as shown by cyclic voltammetry (CV) studies. The high stability of the mixed valence complex [Cu^ICu^II(<b>L–L</b>)₂]³⁺ with respect to disproportionation to [Cu^I₂(<b>L–L</b>)₂]²⁺ and [Cu^II₂(<b>L–L</b>)₂]⁴⁺ is essentially due to a favorable electrostatic term. Cu^II forms with <b>L–L</b> a stable species, with a 1:1 stoichiometric ratio, but, in the absence of crystallographic data, it was impossible to assess whether it is of mono- or dinuclear nature. However, CV studies on an MeCN solution containing equimolar amounts of Cu^II and <b>L–L</b> showed the presence in the reduction scan of two fully reversible waves, separated by about 250 mV, which indicated the presence in solution of a dicopper­(II) double strand helicate complex, [Cu^II₂(<b>L–L</b>)₂]⁴⁺. This work demonstrates that additional interstrand π–π interactions can favor the formation of unusually stable dicopper­(I) and dicopper­(II) helicate complexes

Exploiting Micelle-Driven Coordination To Evaluate the Lipophilicity of Molecules

We present a systematic study based on the calculation of complexation constants between a Zn-complex solubilized in Triton X-100 micellar solutions and a series of linear mono- and dicarboxylic acids, under physiological pH conditions, that allowed the evaluation of the lipophilicity of these molecules. This empirical lipophilicity parameter describes conveniently the partition of organic molecules between hydrophobic microdomains and water. The results can be used to predict the lipophilicity of molecules with similar structure and allows the distinction of intrinsic contributions of the carboxylates and of the methylene groups to the lipophilicity of the molecule

Fabrication of Inkjet-Printed Gold Nanostar Patterns with Photothermal Properties on Paper Substrate

Inkjet printing technology has brought significant advances in patterning various functional materials that can meet important challenges in personalized medical treatments. Indeed, patterning of photothermal active anisotropic gold nanoparticles is particularly promising for the development of low-cost tools for localized photothermal therapy. In the present work, stable inks containing PEGylated gold nanostars (GNSs) were prepared and inkjet printed on a pigment-coated paper substrate. A significant photothermal effect (Δ<i>T</i> ≅ 20 °C) of the printed patterns was observed under near infrared (NIR) excitation of the localized surface plasmon resonance (LSPR) of the GNS with low laser intensity (<i>I</i> ≅ 0.2 W/cm²). Besides the pronounced photothermal effect, we also demonstrated, as an additional valuable effect, the release of a model fluorescent thiol-terminated Bodipy dye (BDP-SH) from the printed gold surface, both under bulk heating and NIR irradiation. These preliminary results suggest the way of the development of a new class of low-cost, disposable, and smart devices for localized thermal treatments combined with temperature-triggered drug release

Self-assembled monolayers of Prussian blue nanoparticles with photothermal effect

<p>A photo-responsive antibacterial surface was prepared grafting non-toxic Prussian blue nanoparticles on a functionalized glass surface. Colloidal Prussian blue was synthesized as nanoparticles with cubic shape and grafted on a polyamine-functionalized SiO₂ surface, obtaining a good coverage and a homogeneous distribution of the nanocubes. Irradiation of these samples in the so-called ‘bio-transparent window’ of the near-infrared allows to exert a triggered antibacterial effect.</p

Optical Method for Predicting the Composition of Self-Assembled Monolayers of Mixed Thiols on Surfaces Coated with Silver Nanoparticles

With a simple optical method, based on UV–vis absorption spectra on glass slides, it is possible to predict the composition of self-assembled monolayers of mixed thiols, grafted on monolayers of silver nanoparticles. Glass slides are modified with the layer-by-layer technique, first forming a monolayer of mercaptopropyltrimethoxysilane, then grafting a monolayer of silver nanoparticles on it. These surfaces are further coated by single or mixed thiol monolayers, by dipping the slides in toluene solutions of the chosen thiols. Exchange constants are calculated for the competitive deposition between the colorless 1-dodecanethiol or PEG5000 thiol and BDP-SH, with the latter being a thiol-bearing molecule containing the strongly absorbing BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) moiety, synthesized on purpose. The constants are calculated by determining the fraction of BDP-SH deposited on the surface from a solution with a given molar fraction, directly measuring the absorption spectra of BDP-SH on the slides. Then, the exchange constant for the competitive deposition between 1-dodecanethiol and PEG5000 thiol is calculated by combining their exchange constants with BDP-SH. This allows to predict the fraction of the two colorless thiols coating the silver nanoparticles slides obtained from a toluene solution with a given molar fraction, for example, of PEG5000 thiol. The correctness of the calculated surface fraction is verified by studying the coating competition between 1-dodecanethiol and a PEG5000 thiol remotely modified with a strongly absorbing fluorescein fragment

Antibacterial Activity of Glutathione-Coated Silver Nanoparticles against Gram Positive and Gram Negative Bacteria

In the present paper, we study the mechanism of antibacterial activity of glutathione (GSH) coated silver nanoparticles (Ag NPs) on model Gram negative and Gram positive bacterial strains. Interference in bacterial cell replication is observed for both cellular strains when exposed to GSH stabilized colloidal silver in solution, and microbicidal activity was studied when GSH coated Ag NPs are (i) dispersed in colloidal suspensions or (ii) grafted on thiol-functionalized glass surfaces. The obtained results confirm that the effect of dispersed GSH capped Ag NPs (GSH Ag NPs) on Escherichia coli is more intense because it can be associated with the penetration of the colloid into the cytoplasm, with the subsequent local interaction of silver with cell components causing damages to the cells. Conversely, for Staphylococcus aureus, since the thick peptidoglycan layer of the cell wall prevents the penetration of the NPs inside the cytoplasm, the antimicrobial effect is limited and seems related to the interaction with the bacterial surfaces. Experiments on GSH Ag NPs grafted on glass allowed us to elucidate more precisely the antibacterial mechanism, showing that the action is reduced because of GSH coating and the limitation of the translational freedom of NPs

Thermal and Chemical Stability of Thiol Bonding on Gold Nanostars

The stability of thiol bonding on the surface of star-shaped gold nanoparticles was studied as a function of temperature in water and in a set of biologically relevant conditions. The stability was evaluated by monitoring the release of a model fluorescent dye, Bodipy-thiol (BDP-SH), from gold nanostars (GNSs) cocoated with poly­(ethylene glycol) thiol (PEG-SH). The increase in the BDP-SH fluorescence emission, quenched when bound to the GNSs, was exploited to this purpose. A maximum 15% dye release in aqueous solution was found when the bulk temperature of gold nanostars solutions was increased to <i>T</i> = 42 °C, the maximum physiological temperature. This fraction reduces 3–5% for temperatures lower than 40 °C. Similar results were found when the temperature increase was obtained by laser excitation of the near-infrared (NIR) localized surface plasmon resonance of the GNSs, which are photothermally responsive. Besides the direct impact of temperature, an increased BDP-SH release was observed upon changing the chemical composition of the solvent from pure water to phosphate-buffered saline and culture media solutions. Moreover, also a significant fraction of PEG-SH was released from the GNS surface due to the increase in temperature. We monitored it with a different approach, that is, by using a coating of α-mercapto-ω-amino PEG labeled with tetramethylrhodamine isothiocyanate on the amino group, that after heating was separated from GNS by ultracentrifugation and the released PEG was determined by spectrofluorimetric techniques on the supernatant solution. These results suggest some specific limitations in the use of the gold–thiolate bond for coating of nanomaterials with organic compounds in biological environments. These limitations come from the duration and the intensity of the thermal treatment and from the medium composition and could also be exploited in biological media to modulate the in vivo release of drugs

Temperature and pH Stimuli-Responsive System Delivers Location-Specific Antimicrobial Activity with Natural Products

Smart materials with controlled stimuli-responsive functions are at the forefront of technological development. In this work, we present a generic strategy that combines simple components, physicochemical responses, and easy fabrication methods to achieve a dual stimuli-responsive system capable of location-specific antimicrobial cargo delivery. The encapsulated system is fabricated by combining a biocompatible inert polymeric matrix of poly(dimethylsiloxane) (PDMS) and a bioactive cargo of saturated fatty acids. We demonstrate the effectiveness of our approach to deliver antimicrobial activity for the model bacteria Escherichia coli. The system responds to two control variables, temperature and pH, delivering two levels of antimicrobial response under distinct combinations of stimuli: one response toward the planktonic media and another response directly at the surface for sessile bacteria. Spatially resolved Raman spectroscopy alongside thermal and structural material analysis reveals that the system not only exhibits ON/OFF states but can also control relocation and targeting of the active cargo toward either the surface or the liquid media, leading to different ON/OFF states for the planktonic and sessile bacteria. The approach proposed herein is technologically simple and scalable, facing low regulatory barriers within the food and healthcare sectors by using approved components and relying on fundamental chemical processes. Our results also provide a proof-of-concept platform for the design and easy fabrication of delivery systems capable of operating as Boolean logic gates, delivering different responses under different environmental conditions

A Molecular Thermometer for Nanoparticles for Optical Hyperthermia

We developed an all-optical method to measure the temperature on gold (nanorods and nanostars) and magnetite nanoparticles under near-infrared and radiofrequency excitation by monitoring the excited state lifetime of Rhodamine B that lies within ≅20 nm from the nanoparticle surface. We reached high temperature sensitivity (0.029 ± 0.001 ns/°C) and low uncertainty (±0.3 °C). Gold nanostars are ≅3 and ≅100 times more efficient than gold nanorods and magnetite nanoparticles in inducing localized hyperthermia

Gold Branched Nanoparticles for Cellular Treatments

Under the action of near-infrared radiation, shape anisotropic gold nanoparticles emit two-photon luminescence and release heat. Accordingly, they have been proposed for imaging, photothermal therapies and thermo-controlled drug delivery. In all these applications particular care must be given to control the nanoparticle – cell interaction and the thermal efficiency of the nanoparticles, while minimizing their intrinsic cytotoxicity. We present here the characterization of the cell interaction of newly developed branched gold nanostars, obtained by laurylsulfobetaine-driven seed-growth synthesis. The study provides information on the size distribution, the shape anisotropy, the cellular uptake and cytotoxicity of the gold nanostars as well as their intracellular dynamic behavior by means of two-photon luminescence imaging, fluorescence correlation spectroscopy and particle tracking. The results show that the gold nanostars are internalized as well as the widely used gold nanorods and are less toxic under prolonged treatments. At the same time they display remarkable two-photon luminescence and large extinction under polarized light in the near-infrared region of the spectrum, 800–950 nm. Gold nanostars appear then a valuable alternative to other elongated or in-homogeneous nanoparticles for cell imaging