Wet chemical synthesis of TGA capped Ag2S nanoparticles and their use for fluorescence imaging and temperature sensing in living cells.

In this work, we describe a simple wet chemical route for preparing silver sulfide nanoparticles (Ag2S) encapsulated with thioglycolic acid (TGA). By using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), energy dispersive X-ray (EDS) microanalysis, transmission electron microscopy (TEM), and dynamic light scattering (DLS), we have found that these nanoparticles were enrobed by TGA molecules and they have an Ag/S ratio nearly equal to 2.2 and a nearly spherical shape with two average size populations. Photoluminescence (PL) spectroscopy has shown that these nanoparticles are highly luminescent, photostable and photobleaching resistant and they emit in the first biologic window with a band peaking in the NIR region at 915 nm. We have demonstrated through a 3-(4,5-dimethyl-thiazol-2yl)-2,5-diphenyltetrazolium bromide (MTT) assay protocol and using U-87 MG human living cells that these nanoparticles are biocompatible with a viability ratio higher than 80% for a concentration equal to 100 µg mL-1. By investigating the effect of pH, ionic strength and thermal quenching on the PL emission, we have shown that these nanoparticles provide a convenient stable tool to measure temperature in the biological range with a relative thermal sensitivity higher than 5% per °C and they may be used as suitable fluorescent probes for living cell imaging and intracellular temperature mapping.

Optical trapping for biosensing: materials and applications.

Since the 70's, when Arthur Ashkin and coworkers demonstrated that optical forces could displace and levitate microsized particles, optical trapping has seen a steady stream of developments and applications, particularly in the biological field. Since that demonstration, optical trapping has been especially exploited as a powerful tool for non-invasive sensitive measurements. The recent development of synthesis routes has further expanded the possibilities of optical trapping in the area of biosensing where new multifunctional particles are used as a single probe. The synergy between the development of new materials and experimental techniques has led to the appearance of numerous studies in which novel biosensing applications are demonstrated. The design of new materials and optical systems to face new challenges makes it necessary to have a clear idea about the latest developments achieved in the field. In this work, we summarize recent experimental advances in biosensing achieved by optical manipulation of micro- and nanoparticles providing a critical review on the state of the art and future prospects.

Assessing Single Upconverting Nanoparticle Luminescence by Optical Tweezers.

We report on stable, long-term immobilization and localization of a single colloidal Er(3+)/Yb(3+) codoped upconverting fluorescent nanoparticle (UCNP) by optical trapping with a single infrared laser beam. Contrary to expectations, the single UCNP emission differs from that generated by an assembly of UCNPs. The experimental data reveal that the differences can be explained in terms of modulations caused by radiation-trapping, a phenomenon not considered before but that this work reveals to be of great relevance.

Gold nanorod assisted intracellular optical manipulation of silica microspheres.

We report on the improvement of the infrared optical trapping efficiency of dielectric microspheres by the controlled adhesion of gold nanorods to their surface. When trapping wavelength was equal to the surface plasmon resonance wavelength of the gold nanorods (808 nm), a 7 times improvement in the optical force acting on the microspheres was obtained. Such a gold nanorod assisted enhancement of the optical trapping efficiency enabled the intracellular manipulation of the decorated dielectric microsphere by using a low power (22 mW) infrared optical trap.

Er:Yb:NaY2F5O up-converting nanoparticles for sub-tissue fluorescence lifetime thermal sensing.

Non-contact thermometry is essential in biomedical studies requiring thermal sensing and imaging with high thermal and spatial resolutions. In this work, we report the potential use of Er:Yb:NaYF4 and Er:Yb:NaY2F5O up-conversion nanoparticles as thermal sensors by means of lifetime based luminescent thermometry. We demonstrate how Er:Yb:NaY2F5O nanocrystals present a higher thermal sensitivity than the Er:Yb:NaYF4 ones and that their lifetime thermal coefficient is comparable to those corresponding to other nano-sized luminescent systems already used for high resolution lifetime fluorescence thermal sensing. We evaluate the potential use of Er:Yb:NaY2F5O nanoparticles as lifetime based thermal probes by providing the first experimental evidence on sub-tissue lifetime fluorescence thermal sensing by using up-conversion nanoparticles in an ex vivo experiment.

Nanoparticles for photothermal therapies.

The current status of the use of nanoparticles for photothermal treatments is reviewed in detail. The different families of heating nanoparticles are described paying special attention to the physical mechanisms at the root of the light-to-heat conversion processes. The heating efficiencies and spectral working ranges are listed and compared. The most important results obtained in both in vivo and in vitro nanoparticle assisted photothermal treatments are summarized. The advantages and disadvantages of the different heating nanoparticles are discussed.

Ion migration assisted inscription of high refractive index contrast waveguides by femtosecond laser pulses in phosphate glass.

In this Letter, we report on the successful fabrication of low loss, high refractive index contrast waveguides via ion migration upon femtosecond laser writing in phosphate glass. Waveguides were produced in two different phosphate glass compositions with high and low La(2)O(3) content. In the La-rich glass, a large refractive index increase in the guiding region was observed due to the incoming migration of La accompanied by the out-diffusion of K. The much smaller refractive index change in the La-less glass is caused by rearrangements of the glass structure. These results confirm the feasibility of adapting the glass composition for enabling the laser writing of high refractive index contrast structures via spatially selective modification of the glass composition.

Optical trapping of NaYF4:Er3+,Yb3+ upconverting fluorescent nanoparticles.

We report on the first experimental observation of stable optical trapping of dielectric NaYF4:Er(3+),Yb(3+) upconverting fluorescent nanoparticles (~26 nm in diameter) using a continuous wave 980 nm single-beam laser. The laser serves both to optically trap and to excite visible luminescence from the nanoparticles. Sequential loading of individual nanoparticles into the trap is observed from the analysis of the emitted luminescence. We demonstrate that the trapping strength and the number of individual nanoparticles trapped are dictated by both the laser power and nanoparticle density. The possible contribution of thermal effects has been investigated by performing trapping experiment in both heavy water and into distilled water. For the case of heavy water, thermal gradients are negligible and optical forces dominate the trap loading behaviour. The results provide a promising path towards real three dimensional manipulation of single NaYF4:Er(3+),Yb(3+) nanoparticles for precise fluorescence sensing in biophotonics experiments.

Upconversion emission obtained in Yb(3+)-Er(3+) doped fluoroindate glasses using silica microspheres as focusing lens.

An intensity enhancement of the green upconversion emission from a codoped Er(3+)-Yb(3+) fluoroindate glass has been obtained by coating the glass surface with silica microspheres (3.8 µm diameter). The microspheres focus an incoming beam (λ ≈ 950 nm) on the surface of the fluoroindate glass. The green emission (λ ≈ 545 nm) of the Er(3+) ions located in the microsphere focus was measured with a microscope in reflection mode, being the peak intensity 4.5 times the emission of the bare substrate. The transversal FWHM of the upconversion spot was experimentally determined by deconvolution with the experimental Point Spread Function of the system, obtaining a value of 309 nm. This value is in good agreement with Finite-Difference Time-Domain simulations taking into account the magnification of the image due to the microsphere.

High-sensitivity fluorescence lifetime thermal sensing based on CdTe quantum dots.

The potential use of CdTe quantum dots as luminescence nano-probes for lifetime fluorescence nano-thermometry is demonstrated. The maximum thermal sensitivity achievable is strongly dependent on the quantum dot size. For the smallest sizes (close to 1 nm) the lifetime thermal sensitivity overcomes those of conventional nano-probes used in fluorescence lifetime thermometry.

Whispering-gallery modes in glass microspheres: optimization of pumping in a modified confocal microscope.

Whispering-gallery modes (WGMs) on Nd3+-doped glass microspheres with a radius of ∼15 µm were measured in a modified confocal microscope, where a dual spatial resolution in both excitation and detection zones was possible. As an alternative to the standard excitation mechanism by an evanescent wave, we used an efficient pumping/detecting scheme, focusing a laser in the microsphere and exciting the Nd3+ ions, whose fluorescent emission produces the WGMs. We have also measured the generated WGMs by changing the detection zone, where higher amplitude resonances were found when exciting in the center and detecting at the edge of the microsphere.

Whispering gallery modes in a glass microsphere as a function of temperature.

Microspheres of Nd3+ doped barium titano silicate glass were prepared and the whispering gallery mode resonances were observed in a modified confocal microscope. A bulk sample of the same glass was calibrated as temperature sensor by the fluorescence intensity ratio technique. After that, the microsphere was heated by laser irradiation process technique in the microscope and the surface temperature was estimated using the fluorescence intensity ratio. This temperature is correlated with the displacement of the whispering gallery mode peaks, showing an average red-shift of 10 pm/K in a wide range of surface temperatures varying from 300 K to 950K. The limit of resolution in temperature was estimated for the fluorescence intensity ratio and the whispering gallery mode displacement, showing an improvement of an order of magnitude for the second method.

Nanocrystals distribution inside the writing lines in a glass matrix using Argon laser irradiation.

Localized modification in strontium barium niobate glass doped with Ho(3+) under laser irradiation has been carried out. The preliminary samples of this study have been fabricated by the melt quenching method and doped with 2.5% mol of Ho(3+). A 3.5W cw multiline Ar-laser has been focused and shifted in a line during laser irradiation. The formation of Strontium Barium Niobate nanocrystals has been confirmed by X-ray diffraction, atomic force microscope image and fluorescence. They have been localized in the irradiation line and change the optical properties of the sample. These nanocrystals have been obtained due to the excitation of the Ho(3+) ions which under nonradiative processes produced the heating of the sample. In this work, it has been demonstrated that the diffusion of the Nb(5+) ions to the border of the irradiated line controls the growth of the nanocrystals in the sample.

Growth of nanocrystals in a Nd3+-Yb3+ codoped oxyfluoride glass by laser irradiation.

A local nanocrystalline formation in a Neodymium-Ytterbium codoped oxyfluoride glass has been obtained. It has been studied the intense emissions around 880 and 975 nm originated from the 4F3/2(Nd3+) and 2F5/2(Yb3+) levels when the glass structure changes to a glass ceramic structure due to the irradiation of the laser beam. The emission spectra before and after the irradiation with 2900 mW reveals that the desvitrification process made by the laser power beam has been successfully achieved. The intensities and lifetime changes of these levels inside and outside the hole made by the laser damage have been analyzed. These results confirm that nanocrystals of betaPbF2 have been created by the laser action confirming that the transition from glass to glass ceramic has been completed. These results are in agreement with the bulk spectroscopic measurements.