High-resolution 3D photopolymerization assisted by upconversion nanoparticles for rapid prototyping applications.

Three-dimensional (3D) rapid prototyping technology based on near-infrared light-induced polymerization of photocurable compositions containing upconversion nanomaterials has been explored. For this aim, the rationally-designed core/shell upconversion nanoparticles NaYF4:Yb3+,Tm3+/NaYF4, with the distinct ultraviolet-emitting lines and unprecedentedly high near-infrared to ultraviolet conversion efficiency of [Formula: see text] have been used. The upconverted ultraviolet photons were capable to efficiently activate photoinitiators contained in light-sensitive resins under moderate intensities of NIR excitation below 10 W cm-2 and induce generation of radicals and photopolymerization in situ. Near infrared-activated polymerization process, both at the millimeter and sub-micron scales, was investigated. Polymeric macro- and microstructures were fabricated by means of near infrared laser scanning photolithography in the volume of liquid photocurable compositions with focused laser light at 975 nm wavelength. Examination of the polymerization process in the vicinity of the nanoparticles shows strong differences in the rate of polymer shell growth on flat and edge nanoparticle sides. This phenomenon mainly defines the resolution of the demonstrated near infrared - ultraviolet 3D printing technology at the micrometer scale level.

The influence of energy migration on luminescence kinetics parameters in upconversion nanoparticles.

The mechanism of upconversion at the nanoscale is still under discussion. In this paper, we report on the experimental results of anti-Stokes luminescence kinetics in the upconversion nanoparticles of ß-NaYF4: 20%Yb3+; 0.6%Tm3+. The parameters of the luminescence kinetics were found to be unambiguously dependent on the number of excitation quanta n, which are necessary for certain transitions between the energy states of thulium ions. The observed correlation has been explained by means of the long-lasting energy migration between the ytterbium ions. The spread in time between the luminescent maxima of the corresponding thulium transitions not only shows the nonlinear character of upconversion, but also reveals the time scale of energy migration as well. From these, we derive that the conventional Förster formalism applied to the estimation of energy transfer efficiency in UCNP-fluorophore pairs can provide misleading results.

Model for Optimization of the UV-A/Riboflavin Strengthening (cross-linking) of the Cornea: Percolation Threshold.

To achieve the maximum level of collagen strengthening within the shortest treatment time possible, we have developed a mathematical model which is used to optimize the process of corneal cross-linking. This model is able to predict the temporal and spatial distribution of generated cross-links within the corneal stroma and hence the increase in the elasticity modulus. Theory predicts corneal strengthening at low radiation intensities and the absence of the strengthening effect at radiation intensities above the threshold level, which agrees with the experimental results. The model takes account of the initial riboflavin concentration and bleaching, light intensity and time of illumination.

Incoherent wavefront reconstruction by a retroemission device.

This Letter addresses wavefront reconstruction by a retroemission device (REM). REM represents a lenslet array mounted on a substrate made of photoluminescent optical material, such as a polymer film impregnated with upconversion nanoparticles. An excitation light wavefront incident on the REM was sampled by the lenslet array piece-wise. Each wavelet at the lenslet aperture was converged into a voxel in the substrate, with its coordinates encoding the angle of incidence and curvature of the wavelet. Photoluminescence excited in the voxel was radiated isotropically, its back-propagating fraction was captured by the lenslet and transformed into a back-propagating wavelet, which contributed to reproduction of the entire incident wavefront with some fidelity. We experimentally proved the wavefront reconstruction based on REM, and present its theoretical model based on a Fresnel-Kirchhoff approximation.

Feasibility study of the optical imaging of a breast cancer lesion labeled with upconversion nanoparticle biocomplexes.

Innovative luminescent nanomaterials, termed upconversion nanoparticles (UCNPs), have demonstrated considerable promise as molecular probes for high-contrast optical imaging in cells and small animals. The feasibility study of optical diagnostics in humans is reported here based on experimental and theoretical modeling of optical imaging of an UCNP-labeled breast cancer lesion. UCNPs synthesized in-house were surface-capped with an amphiphilic polymer to achieve good colloidal stability in aqueous buffer solutions. The scFv4D5 mini-antibodies were grafted onto the UCNPs via a high-affinity molecular linker barstar:barnase (Bs:Bn) to allow their specific binding to the human epidermal growth factor receptor HER2/neu, which is overexpressed in human breast adenocarcinoma cells SK-BR-3. UCNP-Bs:Bn-scFv4D5 biocomplexes exhibited high-specific immobilization on the SK-BR-3 cells with the optical contrast as high as 10:1 benchmarked against a negative control cell line. Breast cancer optical diagnostics was experimentally modeled by means of epi-luminescence imaging of a monolayer of the UCNP-labeled SK-BR-3 cells buried under a breast tissue mimicking optical phantom. The experimental results were analyzed theoretically and projected to in vivo detection of early-stage breast cancer. The model predicts that the UCNP-assisted cancer detection is feasible up to 4 mm in tissue depth, showing considerable potential for diagnostic and image-guided surgery applications.

Quantitative imaging of single upconversion nanoparticles in biological tissue.

The unique luminescent properties of new-generation synthetic nanomaterials, upconversion nanoparticles (UCNPs), enabled high-contrast optical biomedical imaging by suppressing the crowded background of biological tissue autofluorescence and evading high tissue absorption. This raised high expectations on the UCNP utilities for intracellular and deep tissue imaging, such as whole animal imaging. At the same time, the critical nonlinear dependence of the UCNP luminescence on the excitation intensity results in dramatic signal reduction at (∼1 cm) depth in biological tissue. Here, we report on the experimental and theoretical investigation of this trade-off aiming at the identification of optimal application niches of UCNPs e.g. biological liquids and subsurface tissue layers. As an example of such applications, we report on single UCNP imaging through a layer of hemolyzed blood. To extend this result towards in vivo applications, we quantified the optical properties of single UCNPs and theoretically analyzed the prospects of single-particle detectability in live scattering and absorbing bio-tissue using a human skin model. The model predicts that a single 70-nm UCNP would be detectable at skin depths up to 400 µm, unlike a hardly detectable single fluorescent (fluorescein) dye molecule. UCNP-assisted imaging in the ballistic regime thus allows for excellent applications niches, where high sensitivity is the key requirement.

From scattering to wavefronts--what's in between?

PURPOSE: Some optical errors are too localized and random to be detected by commercial wavefront devices and Zernike polynomial expression. We looked beyond aberrations defined by Zernike expression to discuss implications of fine irregularities associated with highly aberrated corneal surfaces and complex surface roughness that can lead to light scattering. METHODS: Most fine irregularities are related to postoperative surface roughness, complexities of corneal ablation, and the laser in situ keratomileusis (LASIK) flap. These can be characterized mathematically by a random function that includes local surface tilts, the correlation radius of irregularities (Ic), surface roughness, and other terms. The Kirchoff method of scatter analysis characterizes fine surface irregularities by replacing each point on the surface with a tangential plane, allowing it to be governed by Snellen and Fresnel laws. RESULTS: The joint action of the continuum of microbeams defines a complex point spread function that can be expressed by the Strehl ratio. Small, highly irregular steep central islands and flap striae may not be adequately detected by Zernike expression and may have a surface irregularity diameter of 0.1 to 2.0 mm and height of 10 to 20 microm that results in a reduced Strehl ratio below 0.8. Laser ablation inhomogeneities may have dimensions of 1 to 10 microm, resulting in a root mean square tilt value approaching 1.0 and a Strehl ratio below 0.5. CONCLUSION: Corneal surface irregularities after laser vision correction may induce significant optical aberrations and distortions apart from classical wavefront or scattering errors. As these may not be detected by commercial wavefront devices, and yet contribute to the degradation of optical performance, alternate techniques should be evaluated to detect and describe these surface irregularities.