In-Brain Multiphoton Imaging of Vaterite Cargoes Loaded with Carbon Dots.

Biocompatible fluorescent agents are key contributors to the theranostic paradigm by enabling real-time in vivo imaging. This study explores the optical properties of phenylenediamine carbon dots (CDs) and demonstrates their potential for fluorescence imaging in cells and brain blood vessels. The nonlinear absorption cross-section of the CDs was measured and achieved values near 50 Goeppert-Mayer (GM) units with efficient excitation in the 775-895 nm spectral range. Mesoporous vaterite nanoparticles were loaded with CDs to examine the possibility of a biocompatible imaging platform. Efficient one- and two-photon imaging of the CD-vaterite composites uptaken by diverse cells was demonstrated. For an in vivo scenario, CD-vaterite composites were injected into the bloodstream of a mouse, and their flow was monitored within the blood vessels of the brain through a cranial window. These results show the potential of the platform for high-brightness biocompatible imaging with the potential for both sensing and simultaneous drug delivery.

Thin-film conformal fluorescent SU8-phenylenediamine.

The SU8 polymer is a negative photoresist widely used to produce high-quality coatings, with controllable thicknesses ranging from nanometers to millimeters, depending on fabrication protocols. Apart from conventional use cases in microelectronics and fluidics, SU8 is quite an attractive platform in nanophotonics. This material, being straightforwardly processed by ultraviolet lithography, is transparent to wavelengths longer than 500 nm. However, introducing fluorescent agents within the SU8 matrix remains a challenge owing to its high hydrophobicity. Here, we develop a process, where colorful quantum dots co-participate in the polymerization process by epoxide amination and become a part of a new fluorescent material - SU8-phenylenediamine. Through comprehensive characterization methods, including XPS and 1H-NMR analyses, we demonstrate that m-PD covalently binds to SU8 epoxy sites with its molecular amine, virtually forming a new material and not just a mixture of two compounds. After characterizing the new strongly fluorescent platform, thin 300 nm films were created on several surfaces, including a conformal coverage of a nanofluidic capillary. This new process provides opportunities to incorporate various functional molecules into optoelectronic devices without the need for multistep deposition and surface functionalization.

Gilded vaterite optothermal transport in a bubble.

Laser beams, capable of controlling the mechanical motion of micron-scale objects, can serve as a tool, enabling investigations of numerous interaction scenarios under full control. Beyond pure electromagnetic interactions, giving rise to conventional gradient forces and radiation pressure, environment-induced thermal effects can play a role and, in certain cases, govern the dynamics. Here we explore a thermocapillary Marangoni effect, which is responsible for creating long-range few hundreds of nano-Newton forces, acting on a bubble around a 'gilded vaterite' nanoparticle. Decorating calcium carbonate spherulite (the vaterite) with gold nanoseeds allows tuning its optical absorption and, as a result, controlling its temperature in a solution. We demonstrate that keeping a balance between electromagnetic and thermal interactions allows creating of a stable micron-scale bubble around the particle and maintaining its size over time. The bubbles are shown to remain stable over minutes even after the light source is switched off. The bubbles were shown to swim toward a laser focus for over 400-µm distances across the sample. Optothermal effects, allowing for efficient transport, stable bubble creation, and particle-fluid interaction control, can grant nano-engineered drug delivery capsules with additional functions toward a theragnostic paradigm shift.

Organic Kainate Single Crystals for Second-Harmonic and Broadband THz Generation.

Organic crystals with unique nonlinear optical properties have been attracting attention owing to their capability to outperform their conventional nonorganic counterparts. Since nonlinear material responses are linked to a crystal's internal microscopic structure, molecular engineering of maximally unharmonic quantum potentials can boost macromolecular susceptibilities. Here, large-scale kainic acid (kainate) single crystals were synthesized, and their linear and nonlinear optical properties were studied in a broad spectral range, spanning the visible to THz spectral regions. The non-centrosymmetric zwitterionic crystallization, molecular structure, and intermolecular arrangement were found to act as additive donor-acceptor domains, enhancing the efficiency of the intrinsic second-order optical nonlinearity of this pure enantiomeric crystal. Molecular simulations and experimental analysis were performed to retrieve the crystals' properties. The crystals were predicted and found to have good transparency in a broad spectral range from the UV to the infrared (0.2-20 µm). Second-harmonic generation was measured for ultrashort pumping wavelengths between 800 and 2400 nm, showing an enhanced response around 600 nm. Broadband THz generation was demonstrated with a detection limited bandwidth of >8 THz along with emission efficiencies comparable to and prevailing those of commercial ZnTe crystals. The broadband nonlinear response and high transparency make kainate crystals extremely attractive for realizing a range of nonlinear optical devices.

Multicolor Phenylenediamine Carbon Dots for Metal-Ion Detection with Picomolar Sensitivity.

Carbon dots keep attracting attention in multidisciplinary fields, motivating the development of new compounds. Phenylenediamine C6H4(NH2)2 dots are known to exhibit colorful emission, which depends on size, composition, and the functional surface groups, forming those structures. While quite a few fabrication protocols have been developed, the quantum yield of phenylenediamine dots still does not exceed 50% owing to undesired fragment formation during carbonization. Here, we demonstrate that an ethylene glycol-based environment allows obtaining multicolor high-quantum-yield phenylenediamine carbon dots. In particular, a kinetic realization of solvothermal synthesis in acidic environments enhances carbonization reaction yield for meta phenylenediamine compounds and leads to quantum yields, exciting 60%. Reaction yield after the product's purification approaches 90%. Furthermore, proximity of metal ions (Nd3+, Co3+, La3+) can either enhance or quench the emission, depending on the concentration. Optical monitoring of the solution allows performing an accurate detection of ions at picomolar concentrations. An atomistic model of carbon dots was developed to confirm that the functional surface group positioning within the molecular structure has a major impact on dots' physicochemical properties. The high performance of new carbon dots paves the way toward their integration in numerous applications, including imaging, sensing, and therapeutics.