Ana-Maria Gabudean

Chitosan-coated triangular silver nanoparticles as a novel class of biocompatible, highly effective photothermal transducers for in vitro cancer cell therapy

One of the relevant directions that nanotechnology is taking nowadays is connected with nanomedicine and specifically related to the use of light and nanoparticles in early diagnosis and effective therapeutics of cancer. Noble-metal nanoparticles can act under laser irradiation as effective photothermal transducers for triggering localized hyperthermia of tumors. In this work we report the performance of newly synthesized chitosan-coated silver nanotriangles (Chit-AgNTs) with strong resonances in near-infrared (NIR) to operate as photothermal agents against a line of human non-small lung cancer cells (NCI-H460). The hyperthermia experiments were conducted by excitation of nanoparticles-loaded cells at 800 nm wavelength from a Ti:Sapphire laser. We found that the rate of cell mortality in the presence of Chit-AgNTs is higher than in the presence of thiolated poly(ethylene) glycol capped gold nanorods (PEG-AuNRs) - a common hyperthermia agent used as reference-, while no destructive effects were noticed on the control sample (cells without nanoparticles) under identical irradiation conditions. Additionally, we conducted cytotoxicity assays and found Chit-AgNTs to be efficiently uptaken by the cells while exhibiting good biocompatibility for healthy human embryonic cells (HEK), which is essential for any in vivo applications. Our results reveal a novel class of biocompatible plasmonic nanoparticles with high potential to be implemented as effective phototherapeutic agents in the battle against cancer.

Solution-phase, dual LSPR-SERS plasmonic sensors of high sensitivity and stability based on chitosan-coated anisotropic silver nanoparticles

There is a need to design highly sensitive plasmonic sensors which impart a good biocompatibility and optical stability to detect low levels of analytes in biological media. In this study we report the formation of chitosan-coated silver nanoparticles of triangular shape in solution by synergistic action of chitosan and trisodium citrate in the presence of silver seeds and ascorbic acid. It has been revealed that these anisotropic silver nanoparticles entrapped in biopolymeric shells are particularly stable and can be successfully used as versatile plasmonic substrates for molecular sensing in solution. In particular, the binding of the probe molecule monolayer (para-aminothiophenol, p-ATP) at the surface of individual chitosan-coated silver nanoparticles was demonstrated both by localized surface plasmon resonance (LSPR) shifts and surface-enhanced Raman scattering (SERS) spectra. While the LSPR-shift assay is operational for signaling molecular binding events, the SERS allows identifying the probe molecules and elucidating its orientation on the metal surface. The proof of concept for biosensing applications and dual functionality of plasmonic platform are evaluated through the combined LSPR-SERS detection of significant biological molecules, adenine. The potential of chitosan–silver nanostructures to extend the standard approach of LSPR sensing by integrating SERS measurements and operate as dual plasmonic sensors would be very attractive for investigation of analytes in biological fluids.

Transparent Plasmonic Nanocontainers Protect Organic Fluorophores against Photobleaching

Numerous research efforts are investigating the possibility of using light interactions with metallic nanoparticles to improve the fluorescence properties of nearby molecules. Few investigations have considered the encapsulation of molecules in metallic nanocavities. In this paper, we present the optical properties of new hybrid nanoparticles consisting of gold nanoshells and fluorescent organic dyes in their liquid cores. Microspectroscopy on single nanoparticle demonstrates that the extinction spectra are in good agreement with Mies theory. Finite difference time domain (FDTD) calculations reveal that excitation and emission radiations are efficiently transmitted through the thin gold nanoshells. Thus, they can be considered as transparent plasmonic nanocontainers for photoactive cores. In agreement with FDTD calculations, measurements show that fluorophores encapsulated in gold nanoshells keep their brightness, but they show fluorescence lifetimes 1 order of magnitude shorter. As a salient consequence, the photoresistance of encapsulated organic dyes is also improved by an order of magnitude. This unusual ultraviolet photoresistance results from the reduced probability of triplet-singlet conversion that eventually exposes dyes to singlet oxygen photodegradation.

Synthesis of PEGylated gold nanostars and bipyramids for intracellular uptake

A great number of works have focused their research on the synthesis, design and optical properties of gold nanoparticles for potential biological applications (bioimaging, biosensing). For this kind of application, sharp gold nanostructures appear to exhibit the more interesting features since their surface plasmon bands are very sensitive to the surrounding medium. In this paper, a complete study of PEGylated gold nanostars and PEGylated bipyramidal-like nanostructures is presented. The nanoparticles are prepared in high yield and their surfaces are covered with a biocompatible polymer. The photophysical properties of gold bipyramids and nanostars, in suspension, are correlated with the optical response of single and isolated objects. The resulting spectra of isolated gold nanoparticles are subsequently correlated to their geometrical structure by transmission electron microscopy. Finally, the PEGylated gold nanoparticles were incubated with melanoma B16-F10 cells. Dark-field microscopy showed that the biocompatible gold nanoparticles were easily internalized and most of them localized within the cells.

Enhancing the Photoluminescence Emission of Conjugated MEH-PPV by Light Processing

We show here that treatment of thin films of conjugated polymers by illumination with light leads to an increase of the intensity of their photoluminescence by up to 42%. The corresponding enhancement of absorbance was much less pronounced. We explain this significant enhancement of photoluminescence by a planarization of the conjugated polymer chains induced by photoexcitations even below the glass transition temperature, possibly due to an increased conjugation length. Interestingly, the photoluminescence remains at the enhanced level for more than 71 h after treatment of the films by illumination with light, likely due to the fact that below the glass transition temperature no restoring force could return the conjugated chains into their initial conformational state.

LED‐activated methylene blue‐loaded Pluronic‐nanogold hybrids for in vitro photodynamic therapy

In this work we introduce a new class of multifunctional photodynamic agents based on the coupling of photosensitizer molecules with noble metal nanoparticles, which can be efficiently activated under low light intensity. The favourable modification of the photophysical properties of methylene blue (MB) in MB-loaded Pluronic-nanogold hybrids (Au-PF127-MB) increases the probability of singlet oxygen generation, which in turn allows the use of a light emitting diode (LED) irradiation source instead of commonly used, more invasive lasers. In this regard, Au-PF127-MB treated human lung carcinoma cells (HTB 177) were irradiated at different light doses, using a 660 nm LED source, the results indicating a dose dependent therapeutic effect, decreasing the cell viability down to 13%. Owing to their effectiveness, biocompatibility and integrated imaging and therapeutic functionalities, Au-PF127-MB could represent an important development in the field of biophotonic applications.

Covalent conjugation of carbon dots with Rhodamine B and assessment of their photophysical properties

The unique photoluminescent properties of carbon dots (CDs) continue to encourage a great interest in their development for a wide range of applications in energy conversion, optoelectronics or sensing. Engaging carbon dots in resonance energy transfer processes with organic dyes could enable the design of functional materials to greatly enhance the performance of solar cells and other optoelectronic devices, or to create new types of sensors. In this work, CDs were functionalized with Rhodamine B (RhB) isothiocyanate, (CD–PEG1500N–Rh) via a simple procedure after surface modification of bare carbon nanoparticles with poly(ethylene glycol) bis(3-aminopropyl) (PEG1500N). The morphology of CD–PEG1500N was ascertained using HR-TEM while the covalent linkage of Rhodamine B at the surface of PEG1500N capped CDs was proved by spectroscopic analysis. The overlap between the emission spectra of CDs and the absorption spectrum of RhB molecules favoured fluorescent (Forster) resonance energy transfer (FRET) from the CDs to the dye molecules. The FRET mechanism was firstly demonstrated by steady-state fluorescence measurements and its efficiency was estimated by photoluminescence lifetime measurements, using the time correlated single photon counting (TCSPC) method with the excitation of picosecond pulse lasers. The synthetic accessibility and the transfer efficiency of these conjugates make them reliable candidates for fluorescent materials to be later used in FRET based sensing platforms and photovoltaic devices.

Study of gold nanorods–protein interaction by localized surface plasmon resonance spectroscopy

In this paper, gold nanorods’ (GNRs) interaction with different proteins (i.e. carbonic anhydrase, lysozyme, ovalbumin and bovine serum albumin (BSA)) at physiological pH is investigated using localized surface plasmon resonance (LSPR) spectroscopy. We observe that the incubation of these proteins at different concentrations with cetyltrimethylammonium bromide-capped GNRs of three aspect ratios induces dramatic changes in the extinction spectra of the nanoparticles. In particular, we correlate the position and shape of the longitudinal LSPR peaks to the ability of the proteins to specifically interact with GNRs’ surface. The different types of behaviour observed are explained by the exposed molecular surface area of the proteins’ cysteine residues as modelled on the basis of their respective X-ray crystallographic data structures. Cysteine is the only amino acid that exhibits an SH group that is well known to have a strong affinity to gold. The presence and the accessibility of such a residue may explain the protein binding to GNRs. The isoelectric point of the proteins is also an important characteristic to take into account, as the electrostatic strength between GNRs and protein explains some of the cases where aggregates are formed.