Imaging Laser-Triggered Drug Release from Gold Nanocages with Transient Absorption Lifetime Microscopy

Nanoparticles have shown promise in loading and delivering drugs for targeted therapy. Many progresses have been made in the design, synthesis, and modification of nanoparticles to fulfill such goals. However, realizing targeted intracellular delivery and controlled release of drugs remains challenging, partly because of the lack of reliable tools to detect the drug-releasing process. In this paper, we applied femtosecond laser pulses to trigger the explosion of gold nanocages (AuNCs) and control the intracellular release of loaded aluminum phthalocyanine (AlPcS) molecules for photodynamic therapy (PDT). AuNCs were found to enhance the encapsulation efficiency and suppress the PDT effect of AlPcS molecules until they were released. More importantly, we discovered that the excited-state lifetimes of the AlPcS–AuNC conjugate (∼3 ps) and free AlPcS (∼11 ps) differ significantly, which was utilized to image the released drug molecules using transient absorption lifetime microscopy with the same laser source. This technique extracts information similar to fluorescence lifetime imaging microscopy but is superior in imaging the molecules that hardly fluoresce or are prone to photobleaching. We further combined a dual-phase lock-in detection technique to show the potential of real-time imaging based on the change in transient optical behaviors. Our method may provide a new tool for investigating nanoparticle-assisted drug delivery and release

Layer-Dependent Ultrafast Carrier and Coherent Phonon Dynamics in Black Phosphorus

Black phosphorus is a layered semiconducting material, demonstrating strong layer-dependent optical and electronic properties. Probing the photophysical properties on ultrafast time scales is of central importance in understanding many-body interactions and nonequilibrium quasiparticle dynamics. Here, we applied temporally, spectrally, and spatially resolved pump–probe microscopy to study the transient optical responses of mechanically exfoliated few-layer black phosphorus, with layer numbers ranging from 2 to 9. We have observed layer-dependent resonant transient absorption spectra with both photobleaching and red-shifted photoinduced absorption features, which could be attributed to band gap renormalization of higher subband transitions. Surprisingly, coherent phonon oscillations with unprecedented intensities were observed when the probe photons were in resonance with the optical transitions, which correspond to the low-frequency layer-breathing mode. Our results reveal strong Coulomb interactions and electron–phonon couplings in photoexcited black phosphorus, providing important insights into the ultrafast optical, nanomechanical, and optoelectronic properties of this novel two-dimensional material

Layer-Dependent Ultrafast Carrier and Coherent Phonon Dynamics in Black Phosphorus

Black phosphorus is a layered semiconducting material, demonstrating strong layer-dependent optical and electronic properties. Probing the photophysical properties on ultrafast time scales is of central importance in understanding many-body interactions and nonequilibrium quasiparticle dynamics. Here, we applied temporally, spectrally, and spatially resolved pump–probe microscopy to study the transient optical responses of mechanically exfoliated few-layer black phosphorus, with layer numbers ranging from 2 to 9. We have observed layer-dependent resonant transient absorption spectra with both photobleaching and red-shifted photoinduced absorption features, which could be attributed to band gap renormalization of higher subband transitions. Surprisingly, coherent phonon oscillations with unprecedented intensities were observed when the probe photons were in resonance with the optical transitions, which correspond to the low-frequency layer-breathing mode. Our results reveal strong Coulomb interactions and electron–phonon couplings in photoexcited black phosphorus, providing important insights into the ultrafast optical, nanomechanical, and optoelectronic properties of this novel two-dimensional material

Optimizing Nonlinear Optical Visibility of Two-Dimensional Materials

Two-dimensional (2D) materials have attracted broad research interests across various nonlinear optical (NLO) studies, including nonlinear photoluminescence (NPL), second harmonic generation (SHG), transient absorption (TA), and so forth. These studies have unveiled important features and information of 2D materials, such as in grain boundaries, defects, and crystal orientations. However, as most research studies focused on the intrinsic NLO processes, little attention has been paid to the substrates underneath. Here, we discovered that the NLO signal depends significantly on the thickness of SiO₂ in SiO₂/Si substrates. A 40-fold enhancement of the NPL signal of graphene was observed when the SiO₂ thickness was varied from 270 to 125 nm under 800 nm excitation. We systematically studied the NPL intensity of graphene on three different SiO₂ thicknesses within a pump wavelength range of 800–1100 nm. The results agreed with a numerical model based on back reflection and interference. Furthermore, we have extended our measurements to include TA and SHG of graphene and MoS₂, confirming that SiO₂ thickness has similar effects on all of the three major types of NLO signals. Our results will serve as an important guidance for choosing the optimum substrates to conduct NLO research studies on 2D materials