Near‐Infrared Excitation/Emission and Multiphoton‐Induced Fluorescence of Carbon Dots

Carbon dots (CDs) have significant potential for use in various fields including biomedicine, bioimaging, and optoelectronics. However, inefficient excitation and emission of CDs in both near‐infrared (NIR‐I and NIR‐II) windows remains an issue. Solving this problem would yield significant improvement in the tissue‐penetration depth for in vivo bioimaging with CDs. Here, an NIR absorption band and enhanced NIR fluorescence are both realized through the surface engineering of CDs, exploiting electron‐acceptor groups, namely molecules or polymers rich in sulfoxide/carbonyl groups. These groups, which are bound to the outer layers and the edges of the CDs, influence the optical bandgap and promote electron transitions under NIR excitation. NIR‐imaging information encryption and in vivo NIR fluorescence imaging of the stomach of a living mouse using CDs modified with poly(vinylpyrrolidone) in aqueous solution are demonstrated. In addition, excitation by a 1400 nm femtosecond laser yields simultaneous two‐photon‐induced NIR emission and three‐photon‐induced red emission of CDs in dimethyl sulfoxide. This study represents the realization of both NIR‐I excitation and emission as well as two‐photon‐ and three‐photon‐induced fluorescence of CDs excited in an NIR‐II window, and provides a rational design approach for construction and clinical applications of CD‐based NIR imaging agents.     

Excitation‐Dependent Photoluminescence from Single‐Carbon Dots

Carbon dots (CDs) are carbon‐based fluorescent nanoparticles that can exhibit excitation‐dependent photoluminescence (PL) “tunable” throughout the entire visible range, interesting for optoelectronic and imaging applications. The mechanism underlying this tunable emission remains largely debated, most prominently being ascribed to dot‐to‐dot variations that ultimately lead to excitation‐dependent ensemble properties. Here, single‐dot spectroscopy is used to elucidate the origin of the excitation‐dependent PL of CDs. It is demonstrated that already single CDs exhibit excitation‐dependent PL spectra, similar to those of the CD ensemble. The single dots, produced by a facile one‐step synthesis from chloroform and diethylamine, exhibit emission spectra with several characteristic peaks differing in emission peak position and spectral width and shape, indicating the presence of distinct emission sites on the CDs. Based on previous work, these emission sites are related to the sp² subregions in the carbon core, as well as the functional groups on the surface. These results confirm that it is possible to integrate and engineer different types of electronic transitions at the nanoscale on a single CD, making these CDs even more versatile than organic dyes or inorganic quantum dots and opening up new routes toward light‐emission engineering.     

Quasi‐Continuous Wave Near‐Infrared Excitation of Upconversion Nanoparticles for Optogenetic Manipulation of C. elegans

Optogenetics is an emerging powerful tool to investigate workings of the nervous system. However, the use of low tissue penetrating visible light limits its therapeutic potential. Employing deep penetrating near‐infrared (NIR) light for optogenetics would be beneficial but it cannot be used directly. This issue can be tackled with upconversion nanoparticles (UCNs) acting as nanotransducers emitting at shorter wavelengths extending to the UV range upon NIR light excitation. Although attractive, implementation of such NIR‐optogenetics is hindered by the low UCN emission intensity that necessitates high NIR excitation intensities, resulting in overheating issues. A novel quasi‐continuous wave (quasi‐CW) excitation approach is developed that significantly enhances multiphoton emissions from UCNs, and for the first time NIR light‐triggered optogenetic manipulations are implemented in vitro and in C. elegans. The approach developed here enables the activation of channelrhodopsin‐2 with a significantly lower excitation power and UCN concentration along with negligible phototoxicity as seen with CW excitation, paving the way for therapeutic optogenetics.     

Upconversion Nanocarriers Encapsulated with Photoactivatable Ru Complexes for Near‐Infrared Light‐Regulated Enzyme Activity

Enzyme activity is important for metabolism, cell functions, and treating diseases. However, remote control of enzyme activity in deep tissue remains a challenge. This study demonstrates near‐infrared (NIR) light‐regulated enzyme activity in living cells based on upconverting nanoparticles (UCNPs) and a photoactivatable Ru complex. The Ru complex is a caged enzyme inhibitor that can be activated by blue light. To prepare a nanocarrier for NIR photoinhibition of enzyme activity, a UCNP and the caged enzyme inhibitors are encapsulated in a hollow mesoporous silica nanoparticle. In such a nanocarrier, the UCNP can harvest NIR light and convert it into blue light, which can activate the caged enzyme inhibitors. This photoactivation process is feasible in deep tissue because of the tissue penetration ability of NIR light. The nanocarrier is compatible to LNCaP, PC3, and SAOS‐2 cells, which show high enzyme expression. NIR irradiation induces release of the inhibitors and inhibition of enzyme activity in living cells. NIR light provides high spatiotemporal resolution to regulate enzyme activity in deep tissue.     

Thermally Activated Photoluminescence in Lead Selenide Colloidal Quantum Dots

The thermal activation processes in PbSe colloidal quantum dots and their influence on the ground‐state exciton emission are discussed. Activation of a dark exciton occurs at 1.4–7 K, assisted by an acoustic phonon coupling. Activation of a bright exciton occurs at 100–200 K, which appears as a sudden change in the photoluminescence band intensity, energy, and full width at half maximum. This activation overcomes the dark–bright‐state splitting, when the activation temperature increases with the decrease of the dots' size. The dark exciton lifetime is found to be ≈6–12 µs at 1.4 K, while the bright exciton lifetime at 300 K evaluated as 450 ns varies slightly with the change in the size of the dots. In addition, the emission quantum yield of these dots, measured at a variety of temperatures when dissolved in various solvents, reveals information about the influence of the environment on the recombination processes.     

Colloidally Stable Silicon Nanocrystals with Near‐Infrared Photoluminescence for Biological Fluorescence Imaging

Luminescent silicon nanocrystals (ncSi) are showing great promise as photoluminescent tags for biological fluorescence imaging, with size‐dependent emission that can be tuned into the near‐infrared biological window and reported lack of toxicity. Here, colloidally stable ncSi with NIR photoluminescence are synthesized from (HSiO_1.5)_n sol–gel glasses and are used in biological fluorescence imaging. Modifications to the thermal processing conditions of (HSiO_1.5)_n sol–gel glasses, the development of new ncSi oxide liberation chemistry, and an appropriate alkyl surface passivation scheme lead to the formation of colloidally stable ncSi with photoluminescence centered at 955 nm. Water solubility and biocompatibility are achieved through encapsulation of the hydrophobic alkyl‐capped ncSi within PEG‐terminated solid lipid nanoparticles. Their applicability to biological imaging is demonstrated with the in‐vitro fluorescence labelling of human breast tumor cells.     

Minimizing the Heat Effect of Photodynamic Therapy Based on Inorganic Nanocomposites Mediated by 808 nm Near‐Infrared Light

Photodynamic therapy (PDT) based on photosensitizers (PSs) constructed with nanomaterials has become popular in cancer treatment, especially oral carcinoma cell. This therapy is characterized by improved PS accumulation in tumor regions and generation of reactive oxygen species (ROS) for PDT under specific excitation. In the selection of near‐infrared (NIR) window, 808 nm NIR light because it can avoid the absorption of water is particularly suitable for the application in PDT. Hence, multiband emissions under a single 808 nm near‐infrared excitation of Nd³⁺‐sensitized upconversion nanoparticles (808 nm UCNPs) have been applied for the PDT effect. 808 nm UCNPs serve as light converter to emit UV light to excite inorganic PS, graphitic carbon nitride quantum dots (CNQDs), thereby generating ROS. In this study, a nanocomposite consisting UCNPs conjugated with poly‐l ‐lysine (PLL) to improve binding with CNQDs is fabricated. According to the research results, NIR‐triggered nanocomposites of 808 nm UCNP‐PLL@CNs have been verified by significant improvement in ROS generation. Consequently, 808 nm UCNP‐PLL@CNs exhibit high capability for ROS production and efficient PDT in vitro and in vivo. Moreover, the mechanism of PDT treatment by 808 nm UCNP‐PLL@CNs is evaluated using the cell apoptosis pathway.     

Far‐Red to Near‐Infrared Carbon Dots: Preparation and Applications in Biotechnology

As novel fluorescent nanomaterials, carbon dots (CDs) exhibit excellent photostability, good biocompatibility, and high quantum yield (QY). Their superior properties make them promising candidates for biomedical assays and therapy. Among them, the red‐emission (>600 nm) CDs have attracted increasing attention in the past years due to their little damage to the biological matrix, deep tissue penetration, and minimum autofluorescence background of biosamples. This Review, summarizes the recent progress of far‐red to near‐infrared (NIR) CDs from the preparation and their biological applications. The challenges in designing far‐red and NIR CDs and their further applications in biomedical fields are also discussed.     

A Colloidal‐Quantum‐Dot‐Based Self‐Charging System via the Near‐Infrared Band

A novel self‐charging platform is proposed using colloidal‐quantum‐dot (CQD) photovoltaics (PVs) via the near‐infrared (NIR) band for low‐power electronics. Low‐bandgap CQDs can convert invisible NIR light sources to electrical energy more efficiently than wider spectra because of reduced thermalization loss. This energy‐conversion strategy via NIR photons ensures an enhanced photostability of the CQD devices. Furthermore, the NIR wireless charging system can be concealed using various colored and NIR‐transparent fabric or films, providing aesthetic freedom. Finally, an NIR‐driven wireless charging system is demonstrated for a wearable healthcare bracelet by integrating a CQD PVs receiver with a flexible lithium‐ion battery and entirely embedding them into a flexible strap, enabling permanent self‐charging without detachment.