RESUMEN
High refractive index, low birefringence photopolymers were created via the radical-mediated, ring opening homopolymerization of 1,2-dithiolane functionalized monomers and were subsequently evaluated as holographic recording media. This investigation systematically characterized the reaction kinetics, thermodynamics, and volume shrinkage of the 1,2-dithiolane homopolymerization as well as the optical transparency, refractive index, birefringence, and holographic performance of multifunctional 1,2-dithiolane functionalized monomers and their resultant polymers. Real-time kinetic and thermodynamic analyses of a monofunctional 1,2-dithiolane monomer, lipoic acid methyl ester (LipOMe), indicated rapid monomer conversion, exceeding 90% in 60 s, with an overall enthalpy of reaction of 18 ± 1 kJ/mol. The ring-opening polymerization resulted in low shrinkage (10.6 ± 0.3 cm3/mol dithiolane) and a significant bulk refractive index increase (0.030 ± 0.003). The resulting photopolymers exhibited high optical transparency, minimal haze, and negligible birefringence, suggesting the potential of 1,2-homopolymers as optical materials. To further explore the specific capabilities for use as high-performance holographic recording applications, several multifunctional monomers were synthesized with the ethanedithiol lipoic acid monomer (EDT-Lip2) selected for experimentation. Holographic diffraction gratings written using this monomer achieved a peak-to-mean refractive index modulation of 0.008 with minimal haze and birefringence.
RESUMEN
While tattooable nanotechnology for in-skin sensing and communication has been a popular concept in science fiction since the 1990s, the first tattooable intradermal nanosensors have only emerged in the past few years, and none have been demonstrated in human skin. We developed a photochromic tattoo that serves as an intradermal ultraviolet (UV) radiometer that provides naked-eye feedback about UV exposure in real time. These small tattoos, or "solar freckles", comprise dermally implanted colorimetric UV sensors in the form of nanoencapsulated leuco dyes that become more blue in color with increasing UV irradiance. We demonstrate the tattoos' functionality for both quantitative and naked-eye UV sensing in porcine skin ex vivo, as well as in human skin in vivo. Solar freckles offer an alternative and complementary approach to self-monitoring UV exposure for the sake of skin cancer prevention. Activated solar freckles provide a visual reminder to protect the skin, and their color disappears rapidly upon removal of UV exposure or application of topical sunscreen. The sensors are implanted in a minimally invasive procedure that lasts only a few seconds, yet remain functional for months to years. These semipermanent tattoos provide an early proof-of-concept for long-term intradermal sensing nanomaterials that provide users with biomedically relevant information in the form of an observable color change.