Conspectus Manipulating the dynamics of dark excited states (DESs), such as higher excited singlet or excited triplet states with no or small radiative decay, are of both fundamental and practical ...interests, an important application being photoactivated diagnosis and therapy (phototheranostics), which include photoacoustic (PA) imaging, photodynamic therapy (PDT), and photothermal therapy (PTT). However, the current understanding of DESs in organic structures is rather limited, thus making any rational manipulation of DES in organic materials very challenging. A DES decays primarily by radiationless transition through two pathways: (i) singlet-to-triplet intersystem crossing (ISC) and (ii) internal conversion (IC) relaxation. The deactivation of a DES via ISC can generate cytotoxic reactive oxygen species (ROS) for PDT, while IC could convert photons into heat for PA imaging and PTT. In this Account, we highlight our research on developing a fundamental understanding of structure–property relationships for manipulation of DESs in organic materials in relation to phototheranostic applications. We describe the application of femtosecond transient absorption (fs-TA) spectroscopy for obtaining valuable insights into the DES dynamics. Afterward, we present our work on DESs in nonrigid molecules that revealed greatly enhanced ISC through geometry twisting, which leads to an innovative pathway to develop organic materials exhibiting external stimuli-responsive reversible switching of ISC. We introduce the concept of smart PDT where highly efficient ISC imparted by geometry twisting in the acidic environment specific to tumors leads to very efficient and highly localized PDT, thus leaving surrounding healthy tissues at a different pH unaffected. This insightful understanding of ISC can lead to the development of more advanced photosensitizers for PDT. Two other emergent concepts from our work presented here are (1) significantly enhanced IC producing strong local heating by combining two-photon absorption with excited state absorption for cumulative multiphoton absorption, thus greatly increasing the strength of the PA signal for nonlinear PA imaging, and (2) shown by an example of an organic molecule, BODIPY, nanoscale charge-transfer state mediated strong IC in aggregate nanoparticles resulting in exceptionally high photothermal conversion efficiency of 61% for both PA and PTT. Some in vivo results of the phototheranostic studies using BODIPY are presented, providing an elegant example of nanoscale manipulation of the excited state dynamics. This Account concludes with a summary and discussion of future perspectives. We hope this Account will deepen the understanding of molecular and nanoscale control of excited state dynamics in organic materials, hopefully enticing a broad range of scientists within different disciplinary areas.
The design, nanochemistry and ttheranostics applications of upconversion nanoparticles (UCNPs) were investigated and applied to health care technology. Among the topics addressed were DNA damage, ...photodynamic therapy for tumor destruction and photoluminescence spectroscopy.
This review summarizes recent progress in the design and applications of cadmium-free quantum dots (Cd-free QDs), with an emphasis on their role in biophotonics and nanomedicine. We first present the ...features of Cd-free QDs and describe the physics and emergent optical properties of various types of Cd-free QDs whose applications are discussed in subsequent sections. Selected specific QD systems are introduced, followed by the preparation of these Cd-free QDs in a form useful for biological applications, including recent advances in achieving high photoluminescence quantum yield (PL QY) and tunability of emission color. Next, we summarize biophotonic applications of Cd-free QDs in optical imaging, photoacoustic imaging, sensing, optical tracking, and photothermal therapy. Research advances in the use of Cd-free QDs for nanomedicine applications are discussed, including drug/gene delivery, protein/peptide delivery, image-guided surgery, diagnostics, and medical devices. The review then considers the pharmacokinetics and biodistribution of Cd-free QDs and summarizes current studies on the in vitro and in vivo toxicity of Cd-free QDs. Finally, we provide perspectives on the overall current status, challenges, and future directions in this field.
This review describes promising laser-based approaches to produce silicon nanostructures, including laser ablation of solid Si targets in residual gases and liquids and laser pyrolysis of silane. ...These methods are different from, and complementary to, widely used porous silicon technology and alternative synthesis routes. One can use these methods to make stable colloidal dispersions of silicon nanoparticles in both organic and aqueous media, which are suitable for a multitude of applications across the important fields of energy and healthcare. Size tailoring allows production of Si quantum dots with efficient photoluminescence that can be tuned across a broad spectral range from the visible to near-IR by varying particle size and surface functionalization. These nanoparticles can also be integrated with other nanomaterials to make multifunctional composites incorporating magnetic and/or plasmonic components. In the energy domain, this review highlights applications to photovoltaics and photodetectors, nanostructured silicon anodes for lithium ion batteries, and hydrogen generation from water. Application to nanobiophotonics and nanomedicine profits from the excellent biocompatibility and biodegradability of nanosilicon. These applications encompass several types of bioimaging and various therapies, including photodynamic therapy, RF thermal therapy, and radiotherapy. The review concludes with a discussion of challenges and opportunities in the applications of laser-processed nanosilicon.
Nanophotonics is an emerging science dealing with the interaction of light and matter on a nanometer scale and holds promise to produce new generation nanophosphors with highly efficient frequency ...conversion of infrared (IR) light. Scientists can control the excitation dynamics by using nanochemistry to produce hierarchically built nanostructures and tailor their interfaces. These nanophosphors can either perform frequency up-conversion from IR to visible or ultraviolet (UV) or down-conversion, which results in the IR light being further red shifted. Nanophotonics and nanochemistry open up numerous opportunities for these photon converters, including in high contrast bioimaging, photodynamic therapy, drug release and gene delivery, nanothermometry, and solar cells. Applications of these nanophosphors in these directions derive from three main stimuli. Light excitation and emission within the near-infrared (NIR) “optical transparency window” of tissues is ideal for high contrast in vitro and in vivo imaging. This is due to low natural florescence, reduced scattering background, and deep penetration in tissues. Secondly, the naked eye is highly sensitive in the visible range, but it has no response to IR light. Therefore, many scientists have interest in the frequency up-conversion of IR wavelengths for security and display applications. Lastly, frequency up-conversion can convert IR photons to higher energy photons, which can then readily be absorbed by solar materials. Current solar devices do not use abundant IR light that comprises almost half of solar energy. In this Account, we present our recent work on nanophotonic control of frequency up- and down-conversion in fluoride nanophosphors, and their biophotonic and nanophotonic applications. Through nanoscopic control of phonon dynamics, electronic energy transfer, local crystal field, and surface-induced non-radiative processes, we were able to produce new generation nanophosphors with highly efficient frequency conversion of IR light. We show that nanochemistry plays a vital role in the design and interface engineering of nanophosphors, providing pathways to expand their range of applications. High contrast in vitro and in vivo NIR-to-NIR up- and down-conversion bioimaging were successfully demonstrated by our group, evoking wide interests along this line. We introduced trivalent gadolinium ions into the lattice of the nanophosphors or into the shell layer of nanophosphors in a core/shell configuration to produce novel nanophosphors for multimodal (MRI and optical) imaging. We also demonstrate the security and display applications using photopatternable NIR-to-NIR and NIR-to-visible frequency up-conversion nanophosphors with appropriately engineered surface chemistry. In addition, we present preliminary results on dye-sensitized solar cells using up-conversion in fluoride lattice-based nanophosphors for IR photon harvesting.
Novel fluorescent, conformationally restricted dipyrromethene boron difluoride (BODIPY) dyes have been prepared by introducing a naphthalenyl group at the meso position of the BODIPY core. These ...BODIPY dyes exhibit increased fluorescence quantum yields compared with dyes that have a meso‐position phenyl group with internal rotation. The absorption and emission wavelengths of such conformationally restricted BODIPY dyes can be easily tuned to the near‐IR range by derivatization through a condensation reaction with benzaldehyde derivatives. The two‐photon absorption properties of these BODIPY dyes were also investigated and the results show that they exhibit increased two‐photon excited fluorescence compared to analogue dyes that contain a phenyl group. The one‐ and two‐photon fluorescence imaging of living cells by using selected BODIPY dyes has been successfully demonstrated.
Green for go! Highly fluorescent BODIPY dyes that emit light ranging from the green to near‐IR region have been synthesized by introducing a bulky naphthalenyl group at the meso position. The one‐ and two‐photon fluorescence imaging of living cells with these dyes has been successfully demonstrated (see graphic).
Abstract
External manipulation of emission colour is of significance for scientific research and applications, however, the general stimulus-responsive colour modulation method requires both ...stringent control of microstructures and continously adjustment of particular stimuli conditions. Here, we introduce pathways to manipulate the kinetics of time evolution of both intensity and spectral characteristics of X-ray excited afterglow (XEA) by regioselective doping of lanthanide activators in core-shell nanostructures. Our work reported here reveals the following phenomena: 1. The XEA intensities of multiple lanthanide activators are significantly enhanced via incorporating interstitial Na
+
ions inside the nanocrystal structure. 2. The XEA intensities of activators exhibit diverse decay rates in the core and the shell and can largely be tuned separately, which enables us to realize a series of core@shell NPs featuring distinct time-dependent afterglow colour evolution. 3. A core/multi-shell NP structure can be designed to simultaneously generate afterglow, upconversion and downshifting to realize multimode time-dependent multicolour evolutions. These findings can promote the development of superior XEA and plentiful spectral manipulation, opening up a broad range of applications ranging from multiplexed biosensing, to high-capacity information encryption, to multidimensional displays and to multifunctional optoelectronic devices.
We introduce a hybrid organic–inorganic system consisting of epitaxial NaYF4:Yb3+/X3+@NaYbF4@NaYF4:Nd3+ (X = null, Er, Ho, Tm, or Pr) core/shell/shell (CSS) nanocrystal with organic dye, indocyanine ...green (ICG) on the nanocrystal surface. This system is able to produce a set of narrow band emissions with a large Stokes-shift (>200 nm) in the second biological window of optical transparency (NIR-II, 1000–1700 nm), by directional energy transfer from light-harvesting surface ICG, via lanthanide ions in the shells, to the emitter X3+ in the core. Surface ICG not only increases the NIR-II emission intensity of inorganic CSS nanocrystals by ∼4-fold but also provides a broadly excitable spectral range (700–860 nm) that facilitates their use in bioapplications. We show that the NIR-II emission from ICG-sensitized Er3+-doped CSS nanocrystals allows clear observation of a sharp image through 9 mm thick chicken breast tissue, and emission signal detection through 22 mm thick tissue yielding a better imaging profile than from typically used Yb/Tm-codoped upconverting nanocrystals imaged in the NIR-I region (700–950 nm). Our result on in vivo imaging suggests that these ICG-sensitized CSS nanocrystals are suitable for deep optical imaging in the NIR-II region.
MXenes, generally referring to two-dimensional (2D) transition-metal carbides, nitrides, and carbonitrides, have received tremendous attention since the first report in 2011. Extensive experimental ...and theoretical studies have unveiled their enormous potential for applications in optoelectronics, photonics, catalysis, and many other areas. Because of their intriguing mechanical and electronic properties, together with the richness of elemental composition and chemical decoration, MXenes are poised to provide a new 2D nanoplatform for advanced optoelectronics. This comprehensive review, intended for a broad multidisciplinary readership, highlights the state-of-the-art progress on MXene theory, materials synthesis techniques, morphology modifications, opto-electro-magnetic properties, and their applications. The efforts exploring the device performance limits, steric configurations, physical mechanisms, and novel application boundaries are comprehensively discussed. The review is concluded with a compelling perspective, outlook as well as non-trivial challenges in future investigation of MXene-based nano-optoelectronics.
PDF
