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Surface sensitivity of lanthanide-doped nanocrystals has a great utility in controlling their optical properties. Surface sensitivity can be principally promoted by energy migration. Herein, we demonstrate that cross-relaxation between lanthanides makes nanocrystals less sensitive to environmental changes. We show that by codoping ytterbium ions (Yb³⁺) and neodymium ions (Nd³⁺) in hexagonal-phase sodium yttrium fluorides, surface sensitivity can be manipulated by energy transfer from Yb³⁺ to Nd³⁺. These findings enhance our understanding of surface quenching of nanocrystals and offer new opportunities in developing highly luminous nanoprobes for molecular sensing and biomedical applications.

The generation, control and transfer of triplet excitons in molecular and hybrid systems is of great interest owing to their long lifetime and diffusion length in both solid-state and solution phase systems, and to their applications in light emission1, optoelectronics, photon frequency conversion and photocatalysis. Molecular triplet excitons (bound electron–hole pairs) are ‘dark states’ because of the forbidden nature of the direct optical transition between the spin-zero ground state and the spin-one triplet levels. Hence, triplet dynamics are conventionally controlled through heavy-metal-based spin–orbit coupling or tuning of the singlet–triplet energy splitting via molecular design. Both these methods place constraints on the range of properties that can be modified and the molecular structures that can be used. Here we demonstrate that it is possible to control triplet dynamics by coupling organic molecules to lanthanide-doped inorganic insulating nanoparticles. This allows the classically forbidden transitions from the ground-state singlet to excited-state triplets to gain oscillator strength, enabling triplets to be directly generated on molecules via photon absorption. Photogenerated singlet excitons can be converted to triplet excitons on sub-10-picosecond timescales with unity efficiency by intersystem crossing. Triplet exciton states of the molecules can undergo energy transfer to the lanthanide ions with unity efficiency, which allows us to achieve luminescent harvesting of the dark triplet excitons. Furthermore, we demonstrate that the triplet excitons generated in the lanthanide nanoparticle–molecule hybrid systems by near-infrared photoexcitation can undergo efficient upconversion via a lanthanide–triplet excitation fusion process: this process enables endothermic upconversion and allows efficient upconversion from near-infrared to visible frequencies in the solid state. These results provide a new way to control triplet excitons, which is essential for many fields of optoelectronic and biomedical research.

Photolabile chelating cages or protecting groups need complex chemical syntheses and require UV, visible, or two-photon NIR light to trigger release. Different cages have different solubilities, reaction rates, and energies required for triggering. Here we show that liposomes containing calcium, adenosine triphosphate, or carboxyfluorescein are tethered to plasmon-resonant hollow gold nanoshells (HGN) tuned to absorb light from 650–950 nm. Picosecond pulses of near infrared (NIR) light provided by a two-photon microscope, or by a stand-alone laser during flow through microfluidic channels, trigger contents release with spatial and temporal control. NIR light adsorption heats the HGN, inducing vapor nanobubbles that rupture the liposome, releasing cargo within milliseconds. Any water-soluble molecule can be released at essentially the same rate from the liposome-HGN. By using liposomes of different composition, or HGN of different sizes or shapes with different nanobubble threshold fluences, or irradiating on or off resonance, two different cargoes can be released simultaneously, one before the other, or in a desired ratio. Calcium release from liposome-HGN can be spatially patterned to crosslink alginate gels and trap living cells. Liposome-HGN provide stable, biocompatible isolation of the bioactive compound from its surroundings with minimal interactions with the local environment.

Multimodal imaging with photoacoustic microscopy (PAM) and optical coherence tomography (OCT) can be an effective method to evaluate the choroidal and retinal microvasculature. To improve the efficiency for visualizing capillaries, colloidal gold nanoparticles (AuNPs) have been applied as a multimodal contrast agent for both OCT and PAM imaging by taking advantage of the strong optical scattering and the strong optical absorption of AuNPs due to their surface plasmon resonance. Ultra-pure AuNPs were fabricated by femtosecond laser ablation, capped with polyethylene glycol (PEG), and administered to 13 New Zealand white rabbits and 3 Dutch Belted pigmented rabbits. The synthesized PEG-AuNPs (20.0 ± 1.5 nm) were demonstrated to be excellent contrast agents for PAM and OCT, and do not demonstrate cytotoxicity to bovine retinal endothelial cells in cell studies. The image signal from the retinal and choroidal vessels in living rabbits was enhanced by up to 82% for PAM and up to 45% for OCT, respectively, by the administered PEG-AuNPs, which enables detection of individual blood vessels by both imaging modalities. The biodistribution study demonstrated the AuNP accumulated primarily in the liver and spleen. Histology and TUNEL staining did not indicate cell injury or death in the lung, liver, kidney, spleen, heart, or eyes up to seven days after AuNP administration. PEG-AuNPs offer an efficient and safe contrast agent for multimodal ocular imaging to achieve improved characterization of microvasculature.

Joint high-resolution multimodal photoacoustic microscopy (PAM) and optical coherence tomography (OCT) was developed to improve the efficiency for visualizing newly developed retinal neovascularization (RNV) and to monitor the dynamic changes of retinal vein occlusion (RVO) in living rabbits. The RNV and RVO models were created in New Zealand rabbits by Rose Bengal laser-induced RVO. Dual modalities imaging equipment, including color fundus photography, fluorescein angiography (FA), OCT, and PAM, was used to image and assess the changes of retinal vasculature. In vivo experimental results exhibited that not only the treatment boundaries and the position of the occluded vasculature but also the structure of individual RNV were markedly observed using PAM platform with great resolution and high image contrast. The laser light energy of 80 nJ was used to induce photoacoustic signal, which is approximately half the energy of the American National Standards Institute safety limit. A cross-sectional structure of RNV was identified with the OCT modality. Furthermore, vibrant transformations in the RNV and the retinal morphology were examined at different times after laser occlusion: days 4, 28, 35, 49, and 90. PAM revealed high contrast and high resolution vascular imaging of the retina and choroid with amplified penetration depth. Through the present custom-built imaging system, both RNV and RVO can be reconstructed and observed in two and three dimensions. A unique dual modality A unique dual modality PAM and OCT can help precisely visualize and distinguish individual microvessels, microvessel depth, and the surrounding anatomy. Thus, the proposed multimodal ocular imaging platform may offer a potential equipment to enhance classification of microvasculature in a reliable and proficient manner in larger rabbit eyes.

Mid-infrared (MIR) microscopy provides rich chemical and structural information about biological samples, without staining. Conventionally, the long MIR wavelength severely limits the lateral resolution owing to optical diffraction; moreover, the strong MIR absorption of water ubiquitous in fresh biological samples results in high background and low contrast. To overcome these limitations, we propose a method that employs photoacoustic detection highly localized with a pulsed ultraviolet laser on the basis of the Grüneisen relaxation effect. For cultured cells, our method achieves water-background suppressed MIR imaging of lipids and proteins at ultraviolet resolution, at least an order of magnitude finer than the MIR diffraction limits. Label-free histology using this method is also demonstrated in thick brain slices. Our approach provides convenient high-resolution and high-contrast MIR imaging, which can benefit the diagnosis of fresh biological samples.

Photoacoustic (PA) imaging is an emerging medical imaging modality that combines optical excitation and ultrasound detection. Because ultrasound scatters much less than light in biological tissues, PA generates high-resolution images at centimeters depth. In recent years, wavelengths in the second near-infrared (NIR-II) window (1000 to 1700 nm) have been increasingly explored due to its potential for preclinical and clinical applications. In contrast to the conventional PA imaging in the visible (400 to 700 nm) and the first NIR-I (700 to 1000 nm) window, PA imaging in the NIR-II window offers numerous advantages, including high spatial resolution, deeper penetration depth, reduced optical absorption, and tissue scattering. Moreover, the second window allows a fivefold higher light excitation energy density compared to the visible window for enhancing the imaging depth significantly. We highlight the importance of the second window for PA imaging and discuss the various NIR-II PA imaging systems and contrast agents with strong absorption in the NIR-II spectral region. Numerous applications of NIR-II PA imaging, including whole-body animal imaging and human imaging, are also discussed.

The marked increase in the incidence of melanoma coupled with the rapid drop in the survival rate after metastasis has promoted the investigation into improved diagnostic methods for melanoma. High-frequency ultrasound (US), optical coherence tomography (OCT), and photoacoustic imaging (PAI) are three potential modalities that can assist a dermatologist by providing extra information beyond dermoscopic features. In this study, we imaged a swine model with spontaneous melanoma using these modalities and compared the images with images of nearby healthy skin. Histology images were used for validation.

Photoacoustic measurements are tested as a possible tool for non invasive quantification of Water/Collagen relative content in InterVertebral Discs (IVDs).

Photoacoustic microscopy (PAM) is an emerging imaging technology that can non-invasively visualize ocular structures in animal eyes. This report describes an integrated multimodality imaging system that combines PAM, optical coherence tomography (OCT), and fluorescence microscopy (FM) to evaluate angiogenesis in larger animal eyes. High-resolution in vivo imaging was performed in live rabbit eyes with vascular endothelial growth factor (VEGF)-induced retinal neovascularization (RNV). The results demonstrate that our multimodality imaging system can non-invasively visualize RNV in both albino and pigmented rabbits to determine retinal pathology using PAM and OCT and verify the leakage of neovascularization using FM and fluorescein dye. This work presents high-resolution visualization of angiogenesis in rabbits using a multimodality PAM, OCT, and FM system and may represent a major step toward the clinical translation of the technology.