Using Two‐Photon Excitation to Control Bending Motions in Molecular‐Crystal Nanorods

Molecular‐crystal nanorods composed of 9‐anthracenecarboxylic acid can undergo reversible bending due to molecular‐level geometry changes associated with the photodimerization of the molecules in the crystal lattice. The use of highly focused near‐IR femtosecond laser pulses results in two‐photon excitation of micrometer‐scale regions and is used to induce transient bends at various locations along the length of a single 200‐nm‐diameter nanorod. Bending can be observed in nanorods with diameters as small as 35 nm, and translational motion of a single nanorod could be induced by sequential bending of longer segments. A kinetic model is presented that quantitatively describes the bending and relaxation dynamics of individual rods. The results of this work show that it is possible to use laser excitation conditions to control the location, rate, and magnitude of photodeformations in these nanorods. The ability to control the motion of these ultrasmall photomechanical structures may be useful for manipulating objects on the nanoscale.     

Precise Two‐Photon Photodynamic Therapy using an Efficient Photosensitizer with Aggregation‐Induced Emission Characteristics

Two‐photon photodynamic therapy (PDT) is able to offer precise 3D manipulation of treatment volumes, providing a target level that is unattainable with current therapeutic techniques. The advancement of this technique is greatly hampered by the availability of photosensitizers with large two‐photon absorption (TPA) cross section, high reactive‐oxygen‐species (ROS) generation efficiency, and bright two‐photon fluorescence. Here, an effective photosensitizer with aggregation‐induced emission (AIE) characteristics is synthesized, characterized, and encapsulated into an amphiphilic block copolymer to form organic dots for two‐photon PDT applications. The AIE dots possess large TPA cross section, high ROS generation efficiency, and excellent photostability and biocompatibility, which overcomes the limitations of many conventional two‐photon photosensitizers. Outstanding therapeutic performance of the AIE dots in two‐photon PDT is demonstrated using in vitro cancer cell ablation and in vivo brain‐blood‐vessel closure as examples. This shows therapy precision up to 5 µm under two‐photon excitation.     

Magneto‐Photoluminescence Based on Two‐Photon Excitation in Lanthanide‐Doped Up‐Conversion Crystal Particles

Experimental studies on magneto‐photoluminescence based on two‐photon excitation in up‐conversion Y₂O₂S:Er, Yb crystal particles are reported. It is found that the up‐conversion photoluminescence generated by two‐photon excitation exhibits magnetic field effects at room temperature, leading to a two‐photon excitation‐induced magneto‐photoluminescence, when the two‐photon excitation exceeds the critical intensity. By considering the spin selection rule in electronic transitions, it is proposed that spin‐antiparallel and spin‐parallel transition dipoles with spin mixing are accountable for the observed magneto‐photoluminescence. Specifically, the two‐photon excitation generates spin‐antiparallel electric dipoles between ⁴S_3/2–⁴I_15/2 in Er³⁺ ions. The antiparallel spins are conserved by exchange interaction within dipoles. When the photoexcitation exceeds the critical intensity, the Coulomb screening can decrease the exchange interaction. Consequently, the spin–orbital coupling can partially convert the antiparallel dipoles into parallel dipoles, generating a spin mixing. Eventually, the populations between antiparallel and parallel dipoles reach an equilibrium established by the competition between exchange interaction and spin–orbital coupling. Applying a magnetic field can break the equilibrium by disturbing spin mixing through introducing spin precessions, changing the spin populations on antiparallel and parallel dipoles and leading to the magneto‐photoluminescence. Therefore, spin‐dependent transition dipoles present a convenient mechanism to realize magneto‐photoluminescence in multiphoton up‐conversion crystal particles.     

Polymer Microstructures through Two‐Photon Crosslinking

Two‐photon crosslinking of polymers (2PC) is proposed as a novel method for the fabrication of freestanding microstructures via two‐photon lithography. During this process in the confocal volume, two‐photon absorption leads to (formal) C,H‐insertion reactions, and consequently to a strictly localized crosslinking of the polymer. To achieve this, the polymer is coated as a solvent‐free (glassy) film onto an appropriate substrate, and the desired microstructure is written by 2PC into this glass. In all regions outside of the focal volume where no two‐photon process occurs, the polymer remains uncrosslinked and can be washed away during a developing process. Using a self‐assembled monolayer containing the same photoreactive group allows covalent attachment of the forming freestanding structures to the substrate, and thus guarantees an improved stability of these structures against shear‐induced detachment. As the two photon process is carried out in the glassy state, in a simple way, multilayer structures can be used to write structures having a varying chemical composition perpendicular to the surface. As an example, the 2PC process is used to build a structure from both protein‐repellent and protein‐adsorbing polymers so that the resulting 3D structure exhibits spatially controlled protein adsorption.     

Self‐Assembly of Biocompatible FeSe Hollow Nanostructures and 2D CuFeSe Nanosheets with One‐ and Two‐Photon Luminescence Properties

Transition metal chalcogenides are investigated for catalyst, intermediary agency, and particular optical properties because of their distinguished electron‐vacancy‐transfer (EVT) process toward different applications. In this work, one convenient approach for making pure‐phased FeSe nanocrystals (NCs) and doped CuFeSe nanosheets (NSs) through a wet chemistry method in mixed solvents is illustrated. The surface modification of each product is realized by using a peptide molecule glutathione (GSH), in which the thiol group (?SH) is ascribed to be the in situ reducer and bonding agency between the crystalline surface and surfactant in whole constructing processes. Due to the functional groups in biological GSH, highly aggregated NCs are rebuilt in the form of an FeSe hollow structure through amino and carboxyl cross‐linking functions through a spontaneous assembly procedure. Owing to the coupling procedure of Cu and Fe in the growth process, it generates enhanced EVT. Additionally, it shows the emission spectra of λ_EM‐PL = 436 nm (FeSe) and 452 nm (CuFeSe) while λ_EX‐PL = 356 nm, it also conveys two‐photon phenomenon while λ_EX‐PL = 720 nm. Moreover, it also shows strong off‐resonant luminescence due to two‐photon absorption, which should be valuable for biological applications.     

Stereotactic Photodynamic Therapy Using a Two‐Photon AIE Photosensitizer

Two‐photon photodynamic therapy (TP‐PDT) is emerging as a powerful strategy for stereotactic targeting of diseased areas, but ideal photosensitizers (PSs) are currently lacking. This work reports a smart PS with aggregation‐induced emission (AIE) feature, namely DPASP, for TP‐PDT with excellent performances. DPASP exhibits high affinity to mitochondria, superior photostability, large two‐photon absorption cross section as well as efficient reactive oxygen species generation, enabling it to achieve photosensitization both in vitro and in vivo under two‐photon excitation. Moreover, its capability of stereotactic ablation of targeted cells with high‐precision is also successfully demonstrated. All these merits make DPASP a promising TP‐PDT candidate for accurate ablation of abnormal tissues with minimal damages to surrounding areas in the treatment of various diseases.     

Two‐Photon Vertical‐Flow Lithography for Microtube Synthesis

Two‐photon vertical‐flow lithography is demonstrated for synthesis of complex‐shaped polymeric microtubes with a high aspect ratio (>100:1). This unique microfluidic approach provides rigorous control over the morphology and surface topology to generate thin‐walled (<1 µm) microtubes with a tunable diameter (1–400 µm) and pore size (1–20 µm). The interplay between fluid‐flow control and two‐photon lithography presents a generic high‐resolution method that will substantially contribute toward the future development of biocompatible scaffolds, stents, needles, nerve guides, membranes, and beyond.     

Photoresponsive Self‐Assembled DNA Nanomaterials: Design,Working Principles,and Applications

Photoresponsive DNA nanomaterials represent a new class of remarkable functional materials. By adjusting the irradiation wavelength, light intensity, and exposure time, various photocontrolled DNA‐based systems can be reversibly or irreversibly regulated in respect of their size, shape, conformation, movement, and dissociation/association. This Review introduces the most updated progress in the development of photoresponsive DNA‐based system and emphasizes their advantages over other stimuli‐responsive systems. Their design and mechanisms to trigger the photoresponses are shown and discussed. The potential application of these photon‐responsive DNA nanomaterials in biology, biomedicine, materials science, nanophotonic and nanoelectronic are also covered and described. The challenges faced and further directions of the development of photocontrolled DNA‐based systems are also highlighted.     

Lipid‐PEG‐Folate Encapsulated Nanoparticles with Aggregation Induced Emission Characteristics: Cellular Uptake Mechanism and Two‐Photon Fluorescence Imaging

Folate functionalized nanoparticles (NPs) that contain fluorogens with aggregation‐induced emission (AIE) characteristics are fabricated to show bright far‐red/near‐infrared fluorescence, a large two‐photon absorption cross section and low cytotoxicity, which are internalized into MCF‐7 cancer cells mainly through caveolae‐mediated endocytosis. One‐photon excited in vivo fluorescence imaging illustrates that these AIE NPs can accumulate in a tumor and two‐photon excited ex vivo tumor tissue imaging reveals that they can be easily detected in the tumor mass at a depth of 400 μm. These studies indicate that AIE NPs are promising alternatives to conventional TPA probes for biological imaging.