Sensitive and High-Throughput Time-Resolved Luminescence Detection of Tetracycline in Milk for Eliminating Background Fluorescence on a Miniaturized Apparatus.

Fluorescence detection has always suffered from high background fluorescence from real samples such as milk. Therefore, cumbersome pretreatments of samples were necessary to remove the fluorescent substances but led to long processing times and low efficiency. Time-resolved luminescence detection is a powerful technique for eliminating short-lived background fluorescence without additional pretreatments. However, the related instruments are usually equipped with high-speed excitation sources and detectors, which are always bulky and expensive. Herein, we developed a low-cost and miniaturized imaging system for high-throughput time-gated luminescence detection. An UV LED array was used to excite multiple samples, the luminescence of which could be detected by a smartphone simultaneously. An analog circuit was designed to synchronize the LED to the mechanical chopper to eliminate the background signals resulting from scattering and short-lived autofluorescence. Compared to other synchronous circuits based on FPGAs and microcontrollers, this analog circuit required no programming and memory. For the first time, high-throughput time-resolved luminescence detection of tetracycline in milk without any separation or enrichment was achieved by utilizing a smartphone as a camera, and the scattered signals and the background fluorescence were eliminated efficiently. The limit of detection reached as low as 53 nM (∼0.024 ppm), lower than the residue limit set by the European Union. This high-throughput time-gated luminescence detection method can be used for quantitative analysis of many real samples with high background fluorescence.

Dual-step reconstruction algorithm to improve microscopy resolution by deep learning.

Deep learning plays an important role in the field of machine learning, which has been developed and used in a wide range of areas. Many deep-learning-based methods have been proposed to improve image resolution, most of which are based on image-to-image translation algorithms. The performance of neural networks used to achieve image translation always depends on the feature difference between input and output images. Therefore, these deep-learning-based methods sometimes do not have good performance when the feature differences between low-resolution and high-resolution images are too large. In this paper, we introduce a dual-step neural network algorithm to improve image resolution step by step. Compared with conventional deep-learning methods that use input and output images with huge differences for training, this algorithm learning from input and output images with fewer differences can improve the performance of neural networks. This method was used to reconstruct high-resolution images of fluorescence nanoparticles in cells.

Microsecond-resolved smartphone time-gated luminescence spectroscopy.

Time-gated luminescence spectra are usually measured by laboratory instruments equipped with high-speed excitation sources and spectrometers, which are always bulky and expensive. To reduce the reliance on expensive laboratory instruments, we demonstrate the first, to the best of our knowledge, use of a smartphone for the detection of time-gated luminescence spectra. A mechanical chopper is used as the detection shutter and an optical switch is placed at the edge of the wheel to convert the chopping signal into a transistor-transistor logic (TTL) signal which is used to control the excitation source and achieve synchronization. The time-gated luminescence spectra at different delay times of Eu(TTA)3 powder and the solutions of Eu-tetracycline complex are successfully detected with a temporal resolution of tens of microseconds by the proposed approach. We believe our approach offers a route toward portable instruments for the measurement of luminescence spectra and lifetimes.

Luminescence lifetime imaging of ultra-long room temperature phosphorescence on a smartphone.

Luminescence lifetime imaging plays an important role in distinguishing the luminescence decay rates in time-resolved luminescence imaging. However, traditional imaging instruments used for detecting lifetimes within milliseconds would be time-consuming when imaging ultra-long luminescence lifetimes over subseconds. Herein, we present an accessible and simple optical system for detecting lifetimes of persistent luminescence. A smartphone integrated with a UV LED, a dichroic mirror, and a lens was used for recording the persistent luminescence. With only a few seconds of data acquisition, a luminescence lifetime image could be processed from the video by exponential fitting of the gray level of each pixel to the delay time. Since this approach only requires single excitation, no synchronous control is needed, greatly simplifying the apparatus and saving the cost. The apparatus was successfully used for ultra-long luminescence lifetime imaging of mouse tissue dyed with a persistent luminescence molecule. This miniaturized apparatus exhibits huge potentiality in time-resolved luminescence imaging for luminescence study and biological detection.

Host Differential Sensitization toward Color/Lifetime-Tuned Lanthanide Coordination Polymers for Optical Multiplexing.

Optical multiplexing based on luminescent materials with tunable color/lifetime has potential applications in information storage and security. However, the available tunable luminescent materials reported so far still suffer from several drawbacks of low efficiency or poor stability, thus restraining their further applications. Herein, we demonstrate a strategy to develop efficient and stable lanthanide coordination polymers (LCPs) with tunable luminescence as a new option for optical multiplexing. Their multicolor emission from green to red and naked-eye-sensitive green emission with tunable lifetime (from ca. 300 to ca. 600 µs) can be controlled by host differential sensitization and energy transfer between lanthanide ions. The quantum efficiencies of developed samples range from around 20 % to 46 % and the luminescence intensity/lifetime appear quite stable in polar solvents up to ten weeks. Furthermore, with the aid of inkjet printing and concepts of luminescence lifetime imaging and time-gated imaging, we illustrate their promising applications of information storage and security in spatial and temporal domains.

Cell-Penetrating Peptides Transport Noncovalently Linked Thermally Activated Delayed Fluorescence Nanoparticles for Time-Resolved Luminescence Imaging.

Luminescent probes and nanoparticles (NPs) with long excited state lifetimes are essential for time-resolved biological imaging. Generally, cell membranes are physiological barriers that could prevent the uptake of many unnatural compounds. It is still a big challenge to prepare biocompatible imaging agents with high cytomembrane permeability, especially for nonmetallic NPs with long-lived luminescence. Herein, an amphiphilic cell-penetrating peptide, F6G6(rR)3R2, was designed to transport hydrophobic fluorophores across cellular barriers. Three classical thermally activated delayed fluorescence (TADF) molecules, 4CzIPN, NAI-DPAC, and BTZ-DMAC, could self-assemble into well-dispersed NPs with F6G6(rR)3R2 in aqueous solution. These NPs showed low cytotoxicity and could penetrate membranes easily. Moreover, long-lived TADF enabled them to be used in time-resolved luminescence imaging in oxygenic environments. These findings greatly expanded the applications of cell-penetrating peptides for delivery of molecules and NPs by only noncovalent interactions, which were more flexible and easier than covalent modifications.

Auto-phase-locked measurement of time-gated luminescence spectra with a microsecond delay.

Time-resolved techniques are widely used in measuring the spectra and lifetimes of the excited states of molecules. However, the relative apparatus always requires gated detector and phase-matching circuitry, which is expensive to implement and maintain. Herein, a novel auto-phase-locked method for time-gated luminescence (TGL) spectra measurement was developed by adjusting the exciting and detecting optical paths to pass through the same chopper wheel, which simultaneously acted as a pulse generator and detecting shutter. This low-cost system needs no phase-matching circuitry or control system. It can detect TGL spectra with a delay time of only microseconds, demonstrating a high temporal resolution for thermally activated delayed fluorescence detection.

Efficient postprocessing technique for fabricating surface nanoscale axial photonics microresonators with subangstrom precision by femtosecond laser.

We demonstrated the subangstrom precise correction of surface nanoscale axial photonics (SNAP) micro-resonators by the femtosecond (fs) laser postprocessing technique for the first time. The internal stress can be induced by fs laser inscriptions in the fiber, causing nanoscale effective radius variation (ERV). However, the obtained ultraprecise fabrication usually undergoes multiple tries. Here, we propose a novel postprocessing technique based on the fs laser that significantly reduces the ERV errors and improves the fabrication precision without iterative corrections. The postexposure process is achieved at the original exposure locations using lower pulse energy than that in the initial fabrication process. The results show that the ERV is nearly proportional to the pulse energy of the postexposure process. The slope of the ERV versus the pulse energy is 0.07 Å/nJ. The maximum of the postprocessed ERV can reach 8.0 Å. The repeatability was experimentally verified by accomplishing the correction on three SNAP microresonators with the precision of 0.75 Å. The developed fabrication technique with fs laser enables SNAP microresonators with new breakthrough applications for optomechanics and filters.

Ultralong luminescence lifetime imaging of edible plant tissue for humidity sensing in food packaging by a smartphone.

The safety of luminescence sensors and probes used in food packaging should be seriously considered, while most luminescence sensors were artificially synthesized with unclear toxicity, and cannot be directly used as indicators that were in contact with food. To overcome this problem, a humidity indicator based on an edible plant tissue was developed without any chemical processing. We found that garlic bulbs could emit significant persistent luminescence after drying at room temperature. The luminescence lifetime decreases from hundreds of milliseconds to tens of milliseconds as humidity increases. The long-lived luminescence could easily be detected through smartphones without any sophisticated instruments. The edible garlic is expected to be used as a humidity indicator in food packaging without worrying about food safety. Furthermore, the interference of scattered light and short-lived fluorescence from foods and packages can be eliminated in time-resolved luminescence imaging, greatly increasing the signal-to-noise ratio.

Heavy-Atom-Free Triplet-Triplet Annihilation Upconversion in Photo-cross-linked Polymer Poly(ethylene glycol) Diacrylate.

Heavy-atom-free triplet-triplet annihilation (TTA) upconversion sensitized by a thermally activated delayed fluorescence (TADF) molecule is investigated in a dried gel made of a photo-cross-linked polymer as the solid-state matrix. The upconversion fluorescence quantum yields, ΦUC, of the solid-gel TTA system at different penetration depths are measured accurately based on a developed internal-reference method. It is found that ΦUC is greatest at the surface and then decreases exponentially with increasing depth, influenced by the substrate absorption. The same process is also performed in a TTA solution at different depths, but a completely different result is obtained; there is little difference for ΦUC. To the best of our knowledge, this is the first time the quantum yields at different transmission depths have been mentioned and calculated experimentally. These results illustrate the importance of accurately measuring the quantum yield of solid-phase TTA upconversion and provide a novel way to improve the solid-phase TTA quantum yield by reducing the thickness of the substrate.

Cell-penetrating peptides noncovalently modified red phosphorescent nanoparticles for high-efficiency imaging.

The application of long-lived phosphorescence probes in time-resolved luminescence imaging is limited by their low quantum yield in aqueous solutions. However, sensitization of thermally activated delayed fluorescence (TADF) materials can compensate for this limitation while addressing the issue of insufficient proportion of their own long lifetime. In this study, we utilized the characteristics of phosphorescence and TADF materials simultaneously by doping the receptor iridium complex PMD-Ir into the donor TADF polymer PCzDP-20 through donor-receptor doping method, and successfully prepared highly efficient red phosphorescent nanoparticles. The quantum yield of the nanoparticles obtained by this method reaches up to 30%, and the luminescence lifetime can reach several thousand nanoseconds. Additionally, due to the low concentration doping of PMD-Ir, the risk of transition metal toxicity is greatly reduced. Furthermore, we used non-covalent modification with amphiphilic cell-penetrating peptides (CPPs) to increase the cell membrane permeability of the nanoparticles. The CPPs modified nanoparticles achieve in vivo confocal imaging of zebrafish and intracellular time-resolved imaging by its significantly improved bioimaging capabilities. The functional nanoparticles designing method fully utilizes the characteristics of PMD-Ir, PCzDP-20, and CPPs, solving the problems of low quantum yield and poor membrane permeability of Ir-complex nanoparticles. This will greatly promote the development of time-resolved luminescence imaging.

Intense Left-handed Circularly Polarized Luminescence in Chiral Nematic Hydroxypropyl Cellulose Composite Films.

Integrating optically active components into chiral photonic cellulose to fabricate circularly polarized luminescent materials has transformative potential in disease detection, asymmetric reactions, and anticounterfeiting techniques. However, the lack of cellulose-based left-handed circularly polarized light (L-CPL) emissions hampers the progress of these chiral functionalizations. Here, this work proposes an unprecedented strategy: incorporating a chiral nematic organization of hydroxypropyl cellulose with robust aggregation-induced emission luminogens to generate intense L-CPL emission. By utilizing N,N-dimethylformamide as a good solvent for fluorescent components and cellulose matrices, this work produces a right-handed chiral nematic structure film with a uniform appearance in reflective and fluorescent states. Remarkably, this system integrates a high asymmetric factor (0.51) and an impressive emission quantum yield (55.8%) into one fascinating composite. More meaningfully, this approach is versatile, allowing for the incorporation of luminogen derivatives emitting multicolored L-CPL. These chiral fluorescent films possess exceptional mechanical flexibility (toughness up to 0.9 MJ m-3) and structural stability even under harsh environmental exposures, making them promising for the fabrication of various products. Additionally, these films can be cast on the fabrics to reveal multilevel and durable anticounterfeiting capabilities or used as a chiral light source to induce enantioselective photopolymerization, thereby offering significant potential for diverse practical applications.

The cis configuration of amino-modified tetraphenylethene for selective detection of single-stranded guanine-rich DNA.

The selectivity and sensitivity of amino-functionalized tetraphenylethene probes (namely Z-N2TPE and E-N2TPE) for ssDNA detection in aqueous solution were investigated. Both Z-N2TPE and E-N2TPE showed high selectivity to guanine-rich ssDNA. The sensitivity was found to be positively related to the DNA length, indicating the longer DNA could binding more probes to cause aggregation induced fluorescence. Z-N2TPE and E-N2TPE could detect guanine-rich ssDNA as short as 5 nt and 10 nt respectively. Theoretical simulation calculation shows that the amino group of the probe could simultaneously bind with guanine and phosphate ester, which contribute to high selectivity. And the cis probe could bind DNA with higher affinity than the trans one, since the two amino groups of Z-N2TPE could synergistically bind DNA while E-N2TPE could bind DNA with only one amino group.

Spectrally resolved luminescence lifetime detection for measuring the energy splitting of the long-lived excited states.

Molecular motion plays an important role in the reverse intersystem crossing of thermally activated delayed fluorescence (TADF) materials, since the conformation varies as the molecule vibrates, leading to potential changes in the energies of excited states. Although many theoretical simulations have researched the relationship between the excited states and the molecular conformations, there are still few experimental results showing the energy level difference between different long-lived excited states. Herein, a novel method for measuring spectrally resolved luminescence lifetimes is proposed to detect the energy splitting of the long-lived excited states of a classical TADF molecule, BTZ-DMAC. A set of the time-gated luminescence spectra with different delay times were captured by a spectrograph equipped on an auto-phase-locked system, and then used for lifetime analysis at each wavelength. Unlike traditional measurement techniques, the proposed novel method does not require ultrafast laser, high-speed detector and any phase matching circuitry, thus significantly reducing the cost. This method revealed a definite energy gap between the two excited states of BTZ-DMAC with different lifetimes, indicating different conformations caused by molecular vibration. This low-cost method could be also used to detect many other luminescence materials for investigating the detail mechanisms of multiple excited states.

Auto-Phase-Locked Time-Resolved Luminescence Detection: Principles, Applications, and Prospects.

Time-resolved luminescence measurement is a useful technique which can eliminate the background signals from scattering and short-lived autofluorescence. However, the relative instruments always require pulsed excitation sources and high-speed detectors. Moreover, the excitation and detecting shutter should be precisely synchronized by electronic phase matching circuitry, leading to expensiveness and high-complexity. To make time-resolved luminescence instruments simple and cheap, the automatic synchronization method was developed by using a mechanical chopper acted as both of the pulse generator and detection shutter. Therefore, the excitation and detection can be synchronized and locked automatically as the optical paths fixed. In this paper, we first introduced the time-resolved luminescence measurements and review the progress and current state of this field. Then, we discussed low-cost time-resolved techniques, especially chopper-based time-resolved luminescence detections. After that, we focused on auto-phase-locked method and some of its meaningful applications, such as time-gated luminescence imaging, spectrometer, and luminescence lifetime detection. Finally, we concluded with a brief outlook for auto-phase-locked time-resolved luminescence detection systems.

Smartphone-based apparatus for measuring upconversion luminescence lifetimes.

Luminescence lifetime detection plays an important role in time-resolved detection and research. However, the traditional instruments always require expensive detectors such as time-correlated single photon counter or streak camera. Herein, a low-cost and miniaturized apparatus for measuring upconversion luminescence lifetimes was developed by using a smartphone equipped with a 980 nm CW laser and a motor. When the motor was driving the sample circling at a high linear velocity, the excited sample would emit a luminescence arc, which could be photographed by the phone camera. The rotating rate could be measured by a tuner APP and then used for transferring arc length to delay times. By analyzing the grayscale distribution of the luminescence arc, the luminescence decay curve was obtained, which was then used for exponential fit and calculating lifetimes. The images captured by different smartphones revealed similar lifetime values, suggesting a wide universality of this method. The whole system was not only remarkably cheaper but also more miniaturized than traditional instruments for measuring luminescence lifetimes, indicating the promising applications in point of care testing for time-resolved luminescence detection for bioanalysis and disease diagnosis.

Hydrophilic, Red-Emitting, and Thermally Activated Delayed Fluorescence Emitter for Time-Resolved Luminescence Imaging by Mitochondrion-Induced Aggregation in Living Cells.

Thermally activated delayed fluorescence (TADF) materials have provided new strategies for time-resolved luminescence imaging (TRLI); however, the development of hydrophilic TADF luminophores for specific imaging in cells remains a substantial challenge. In this study, a mitochondria-induced aggregation strategy for TRLI is proposed with the design and utilization of the hydrophilic TADF luminophore ((10-(1,3-dioxo-2-phenyl-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)-9,9-dimethyl-9,10-dihydroacridin-2-yl)methyl)triphenylphosphonium bromide (NID-TPP). Using a nonconjugated linker to introduce a triphenylphosphonium (TPP+) group into the 6-(9,9-dimethylacridin-10(9H)-yl)-2-phenyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (NID) TADF luminophore preserves the TADF emission of NID-TPP. NID-TPP shows clear aggregation-induced delayed fluorescence enhancement behavior, which provides a practical strategy for long-lived delayed fluorescence emission in an oxygen-containing environment. Finally, the designed mitochondrion-targeting TPP+ group in NID-TPP induces the adequate accumulation of NID-TPP and results in the first reported TADF-based time-resolved luminescence imaging and two-photon imaging of mitochondria in living cells.

An AIE-based metallo-supramolecular assembly enabling an indicator displacement assay inside living cells.

We report a novel metallo-supramolecular assembly (Z/E-TPE2CyZn-PV), which consists of a tetraphenylethene (TPE)-based dinuclear Zn2+-cyclen complex and pyrocatechol violet (PV). The assembly is developed for indicator-displacement assays (IDAs) inside living cells.

Organic emitter integrating aggregation-induced delayed fluorescence and room-temperature phosphorescence characteristics, and its application in time-resolved luminescence imaging.

Thermally activated delayed fluorescence (TADF) with a substantially long lifetime furnishes a new paradigm in developing probes for time-resolved imaging. Herein, a novel TADF fluorophore, namely, PXZT, with terpyridine as the acceptor and phenoxazine (PXZ) as the donor, was rationally designed and synthesized. The new compound shows typical thermally activated delayed fluorescence, aggregation-induced emission and crystallization-induced room-temperature phosphorescence (RTP). The coordination of PXZT with a zinc ion causes the quenching of the fluorescence of PXZT due to the enhanced intramolecular charge transfer of the resulting complex ZnPXZT1. With the dissociation of the ZnPXZT1 to release PXZT and the subsequent in situ hydrophobic aggregation of the free PXZT to resist the influence of oxygen, the TADF emission of PXZT is recovered. This zinc-assisted process is successfully used for time-resolved imaging of HeLa and 3T3 cells. This work presents a simple and effective strategy for time-resolved imaging by in situ forming TADF aggregates to turn on the TADF emission.

An efficient exciton harvest route for high-performance OLEDs based on aggregation-induced delayed fluorescence.

We managed to integrate the features of aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF), by introducing a fluorine atom into the quinoxaline system for highly efficient fluorescent OLEDs. With a purposive design and well-controlled synthesis, two novel AIE-TADF compounds were demonstrated and characterized. Monofluoro-substituted SFDBQPXZ exhibited high efficiencies in a doped OLED with a maximum EQE of 23.5%, a maximum current efficiency (CE) of 78.3 cd A-1 and a maximum power efficiency (PE) of 91.1 lm W-1. Noteworthily, by employing SFDBQPXZ as an orange emitter in a non-doped device, we have realized a considerably high EQE over 10%. The high efficiency and low roll-off in the doped or non-doped devices make our strategy promising and meaningful for OLED applications.