Gold Nanostars Embedded in PDMS Films: A Photothermal Material for Antibacterial Applications.

Bacteria infections and related biofilms growth on surfaces of medical devices are a serious threat to human health. Controlled hyperthermia caused by photothermal effects can be used to kill bacteria and counteract biofilms formation. Embedding of plasmonic nano-objects like gold nanostars (GNS), able to give an intense photothermal effect when irradiated in the NIR, can be a smart way to functionalize a transparent and biocompatible material like polydimethylsiloxane (PDMS). This process enables bacteria destruction on surfaces of PDMS-made medical surfaces, an action which, in principle, can also be exploited in subcutaneous devices. We prepared stable and reproducible thin PDMS films containing controllable quantities of GNS, enabling a temperature increase that can reach more than 40 degrees. The hyperthermia exerted by this hybrid material generates an effective thermal microbicidal effect, killing bacteria with a near infrared (NIR) laser source with irradiance values that are safe for skin.

Modified Mesoporous Silica Nanoparticles with a Dual Synergetic Antibacterial Effect.

Application of mesoporous silica nanoparticles (MSNs) as antifouling/antibacterial carriers is limited and specifically with a dual synergetic effect. In the present work, MSNs modified with quaternary ammonium salts (QASs) and loaded with the biocide Parmetol S15 were synthesized as functional fillers for antifouling/antibacterial coatings. From the family of the MSNs, MCM-48 was selected as a carrier because of its cubic pore structure, high surface area, and high specific pore volume. The QASs used for the surface modification of MCM-48 were dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and dimethyltetradecyl[3-(triethoxysilyl)propyl]ammonium chloride. The QAS-modified MCM-48 reveals strong covalent bonds between the QAS and the surface of the nanoparticles. The surface functionalization was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, and ζ-potential measurements. Additional loading of the QAS-modified MCM-48 with a commercially available biocide (Parmetol S15) resulted in a synergetic dual antibacterial/antifouling effect. Either loaded or unloaded QAS-modified MSNs exhibited high antibacterial performance confirming their dual activity. The QAS-modified MCM-48 loaded with the biocide Parmetol S15 killed all exposed bacteria after 3 h of incubation and presented 100% reduction at the antibacterial tests against Gram-negative and Gram-positive bacteria. Furthermore, the QAS-modified MCM-48 without Parmetol S15 presented 77-89% reduction against the exposed Gram-negative bacteria and 78-94% reduction against the exposed Gram-positive bacteria. In addition, the modified MCM-48 was mixed with coating formulations, and its antifouling performance was assessed in a field test trial in northern Red Sea. All synthesized paints presented significant antifouling properties after 5 months of exposure in real seawater conditions, and the dual antifouling effect of the nanoparticles was confirmed.

Silane-coated magnetic nanoparticles with surface thiol functions for conjugation with gold nanostars.

Small (d∼ 8 nm) magnetite nanoparticles, Fe3O4NP, are prepared and coated with mercaptopropyl trimethoxysilane (MPTS) to form Fe3O4NP@MPTS. In the coating step controlled MPTS/Fe3O4NP molar ratios are used, ranging from 1 to 7.8 × 10(4). The total quantity of MPTS per Fe3O4NP is determined by SEM-EDS analysis and the average number of free, reactive -SH groups per Fe3O4NP is calculated by a colorimetric method. At very low molar ratios MPTS forms a submonolayer on the Fe3O4NP surface with all -SH free to react, while on increasing the MPTS/Fe3O4NP molar ratio the (CH3O)3Si- groups of MPTS polymerize, forming a progressively thicker shell, in which only a small fraction of the -SH groups, positioned on the shell surface, is available for further reaction. The MPTS shell reduces the magnetic interactions occurring between the magnetite cores, lowering the occurrence and strength of collective magnetic states, with Fe3O4NP@MPTS showing the typical behaviour expected for a sample with a mono-modal size distribution of superparamagnetic nanoparticles. Interaction of Fe3O4NP@MPTS with gold nanostars (GNS) was tested, using both Fe3O4NP@MPTS with a MPTS submonolayer and with increasing shell thickness. Provided that a good balance is used between the number of available -SH and the overall size of Fe3O4NP@MPTS, the free thiols of such nanoparticles bind GNS decorating their surface, as shown by UV-Vis spectroscopy and TEM imaging.

Nanoscale phase separation in coated Ag nanoparticles.

In this paper we report the structural investigation of cysteine and glutathione capped Ag nanoparticles (NPs) by means of transmission electron microscopy (TEM), synchrotron X-ray diffraction (XRD) and pair distribution function (PDF) analysis. The combined use of these probes allowed us to observe the presence of two crystal structures in the coated AgNPs, i.e., the cubic and the hexagonal crystal structures of Ag. In particular, it was possible to demonstrate that the coated AgNPs are a nanoscale phase separated system where the two phases coexist within the single grain. In addition, the relative bulk amount of the fcc and hcp phases has been estimated and a possible correlation with the capping agent proposed.

Multicomponent polymeric micelles based on polyaspartamide as tunable fluorescent pH-window biosensors.

PHEA-PEG(5000)-C(16) is a polyaspartamide polymer with appended hydrophilic PEG(5000) functions and hydrophobic n-C(16) units forming biocompatible micelles with a CAC as low as 1.8 × 10(-7) M. The protonation and acidity constants of the polymer's amino and carboxylic groups have been determined by potentiometric titrations at five different concentrations higher than CAC, finding concentration-independent values. Viscosity and polarity of the micellar core have been investigated by means of fluorescent probes, finding local values comparable to those of pure toluene and to the core of sodium dodecyl sulphate micelles, independently on the protonation degree of the polymer. The fluorophore pyrene, the lipophilic N,N'-dimethyl-N"-dodecylamine and 2-dodecylpyridine self-assemble in the hydrophobic core of PHEA-PEG(5000)-C(16) micelles originating a micellar device that behaves as a rare "off-on-off" fluorescence sensor for pH windows, with no interference by the amino and carboxylic functions of the polymer. The "on" state of the sensor includes the physiological 6-8 pH interval, and can be finely shifted in both directions of the pH axis by comicellization of charged cosurfactants. Dialysis experiments demonstrate that the micellar device exibits an efficient retention ability of all molecular components, including cosurfactants, thus candidating for in vivo use.

Self-assembled monolayers of silver nanoparticles firmly grafted on glass surfaces: low Ag+ release for an efficient antibacterial activity.

A two-step, easy synthetic strategy in solution has been optimized to prepare authentic monolayers of silver nanoparticles (NP) on MPTS-modified glass surfaces, that were investigated by AFM imaging and by quantitative silver determination techniques. NP in the monolayers remain firmly grafted (i.e. not released) when the surfaces are exposed to air, water or in the physiological conditions mimicked by phosphate saline buffer, as UV-Vis spectroscopy and AFM studies demonstrate. About 15% silver release as Ag(+) ions has been found after 15days when the surfaces are exposed to water. The released silver cations are responsible of an efficient local microbicidal activity against Escherichia coli and Staphylococcus aureus bacterial strains.

A micellar multitasking device: sensing pH windows and gauging the lipophilicity of drugs with fluorescent signals.

A multitasking fluorescent device can be obtained by forming micelles of Triton X-100, containing a lipophilic macrocyclic Cu(2+) complex and the coordinating fluorophore Coumarin 343 (C343), which features a COOH moiety. At low pH the two micellised components do not interact, and the fluorescence of Courmarin 343 (C343) is intense. At intermediate pH, C343 is deprotonated and coordinates to the Cu(2+) centre in its apical position, with fluorescence quenching. At higher pH the deprotonated C343 is displaced from Cu(2+) by the formation of an OH(-) complex, and the fluorescence is revived. This allows the system to carry out its first task as it behaves as an "on-off-on" fluorescent sensor for pH windows. The "off" part of the window ranges from pH 6 to 8. In this interval, in which the carboxylate form of C343 is apically coordinated to the Cu(2+) complex inside micelles, the device carries out its second task, that is, it behaves as a gauge for lipophilicity. For pHs between 6 and 8, molecules containing a COOH group are in their COO(-) form and distribute between bulk water and micelles proportionally to their lipophilicity. Upon entering the micelle, their COO(-) moiety competes for coordination with C343, displacing it from the Cu(2+) centre, and this results in fluorescence revival, the intensity of which is also proportional to the lipophilicity of the examined molecule. We have chosen the physiological pH value (7.4) as the working pH, and we have examined the lipophilicity of fatty acids and of the widely used family of non-steroidal anti-inflammatory drugs (NSAIDs). The device successfully measures their lipophilicity, expressing it with an "off-on" type fluorescent signal, as demonstrated by the correlation of the fluorescence increase with the logarithmic water/octanol partition coefficient (log P) and with the difference between the pK(a) observed in micelles and that measured in water for NSAIDs.

Smoothly shifting fluorescent windows: a tunable "off-on-off" micellar sensor for pH.

The position of the window in an "off-on-off" fluorescent pH sensor may be shifted at will along a pH axis by changing the overall charge of the micellar container. This is obtained by using non-ionic Triton X-100 as the surfactant, and by increasing the molar fraction of the anionic sodium dodecyl sulfate (chi(SDS)) as co-surfactant, with pyrene as the fluorophore and a lipophilic tertiary amine and a lipophilic pyridine as pH-switchable quenchers. As the negative micellar charge increases by increasing chi(SDS), the observed pKa of the protonated bases move to higher pH values, followed by the dumb-bell shaped "off-on-off" fluorescence intensity vs. pH profile.

The Cu(II) complex of a C-lipophilized 13aneN4 macrocycle with an additional protonable amino group as micellar anion receptor.

Three 13aneN4 macrocyclic ligands have been prepared bearing a -CH(2)NHR side arm (R = H, n-C(5)H(11), n-C(10)H(21)) on a carbon atom. When Cu(2+) is complexed in the macrocyclic ring, the amino group of the side arm undergoes an acid-base protonation equilibrium but it is not able to coordinate apically the metal cation even when it is deprotonated. The Cu(2+) complex with the ligand bearing the longest appended aliphatic chain is fully confined inside Triton X-100 micelles, and its ability to bind and sequestrate a series of anions inside micelles has been studied at two different pH values, i.e. both with protonated and neutral side-arm amino group. The favourable role played by the protonated amino group in the side arm has been demonstrated.

Fluorescent sensors for Hg(2+) in micelles: a new approach that transforms an ON-OFF into an OFF-ON response as a function of the lipophilicity of the receptor.

A new approach to the use of micelles in the fluorescent sensing of metal cations is proposed and applied to the case of Hg(2+). We demonstrate how it is possible to transform a system from an ON-OFF to an OFF-ON sensor by changing the length of the chain used to lipophilise a ligand that resides inside TritonX-100 micelles together with pyrene as the fluorophore. Three tetrathia-monoaza macrocyclic ligands have been synthesised with the same ring but functionalised on the nitrogen atom with a methyl (C1-NS4), an n-butyl (C4-NS4) or an n-dodecyl (C12-NS4) chain. The three ligands have been fully characterised in water containing TritonX-100 micelles by means of potentiometric titrations and their apparent protonation and complexation constants with Hg(2+) were determined. On the basis of the distribution diagrams obtained, the more lipophilic C12-NS4 has been developed as an ON-OFF fluorescent sensor for mercury: working at pH<4, in the absence of Hg(2+) the ligand is inside the micelles, protonated and non-quenching, while on addition of mercury the [C12-NS4Hg](2+) complex forms which remains inside the micelles and is quenching. On the other hand, the ligand of intermediate chain length, C4-NS4, can be used to obtain an OFF-ON sensor at 7.07.0 the ligand is unprotonated, it stays inside the micelles and is quenching, while addition of Hg(2+) in the 7.0-9.5 pH range results in the formation of [C4-NS4Hg](2+), which is hydrophilic enough to leave the micelles and to be released into the bulk solution where it is no longer capable of quenching pyrene fluorescence. Additional studies on C1-NS4, C3-NS4 and C8-NS4 indicate that the optimal chain length to observe this OFF-ON behaviour is C(3)-C(4).