Programmable multimode optical encryption of advanced printable security inks by integrating structural color with Down/Up- conversion photoluminescence.

Optical information encryption with high encoding capacities can significantly boost the security level of anti-counterfeiting in the scenario of guaranteeing the authenticity of a wide scope of common and luxury goods. In this work, a novel counterfeiting material with high-degree complexity is fabricated by microencapsulating cholesteric liquid crystals and triplet-triplet annihilation upconversion fluorophores to integrate structural coloration with fluorescence and upconversion photoluminescence. Moreover, the multimode security ink presents tailorable optical behaviors and programmable abilities on flexible substrates by various printing techniques, which offers distinct information encryption under different optical modes. The advanced strategy provides a practical versatile platform for high-secure-level multimode optical inks with largely enhanced encoding capacities, programmability, printability, and cost-effectiveness, which manifests enormous potentials for information encryption and anti-counterfeiting technology.

Photochemically deoxygenating micelles for protecting TTA-UC against oxygen quenching.

Pluronic F127, P123 and cross-linked F127 diacrylate micelles are photochemically deoxygenating nanocapsules in which oxygen could be removed by photochemical reaction with a surfactant and efficient triplet-triplet annihilation photon upconversion (TTA-UC) can be achieved in air. The efficiency of TTA-UC under air is comparable to that under deoxygenated conditions.

Multi-wavelength excited triplet-triplet upconversion microcrystals based on hot-band excitation for optical information encryption.

Multi-wavelength hot-band excitation, forbidden in the conventional Stokes fluorescence mechanism, is found to be available with cascading triplet-triplet annihilation upconversion (TTA-UC). Selective excitation of Pt(II)octaethylporphyrin (PtOEP) by diode lasers with wavelengths of 532 nm, 589 nm, 635 nm, 655 nm, and 671 nm respectively can all induce 9,10-diphenylanthracene (DPA) to emit blue upconversion, with the maximum anti-Stokes shift of 0.95 eV in the microcrystals exposed to air. Whether the zero-vibrational energy level excitation or the hot-vibrational energy level excitation in the ground state, the PtOEP/DPA pair showed triplet-triplet energy transfer (TTET) efficiencies approaching ∼95%. The doped microcrystal samples without encapsulation can emit blue upconversion from green/yellow/red excitation with stability for ∼20 days under atmospheric conditions, demonstrating their potential applications in multiple information encryption.

Lateral Heterostructured Vis-NIR Photodetectors with Multimodal Detection for Rapid and Precise Classification of Glioma.

Precise diagnosis of the boundary and grade of tumors is especially important for surgical dissection. Recently, visible and near-infrared (Vis-NIR) absorption differences of tumors are demonstrated for a precise tumor diagnosis. Here, a template-assisted sequential printing strategy is investigated to construct lateral heterostructured Vis-NIR photodetectors, relying on the up-conversion nanoparticles (UCNPs)/perovskite arrays. Under the sequential printing process, the synergistic effect and co-confinement are demonstrated to induce the UCNPs to cover both sides of the perovskite microwire. The side-wrapped lateral heterogeneous UCNPs/perovskite structure exhibits more satisfactory responsiveness to Vis-NIR light than the common fully wrapped structure, due to sufficient visible-light-harvesting ability. The Vis-NIR photodetectors with R reaching 150 mA W-1 at 980 nm and 1084 A W-1 at 450 nm are employed for the rapid classification of glioma. The detection accuracy rate of 99.3% is achieved through a multimodal analysis covering the Vis-NIR light, which provides a reliable basis for glioma grade diagnosis. This work provides a concrete example for the application of photodetectors in tumor detection and surgical diagnosis.

Single-Mode-Tuned Tricolor Emissions of Upconversion/Afterglow Hybrids for Anticounterfeiting Applications.

This work presents a highly secure anticounterfeiting strategy based on upconversion/afterglow hybrids with tricolor emissions tuned by a single 975 nm laser. The hybrids are composed of NaYF4:Yb/Tm and NaYF4:Yb/Er microrods and CaS:Eu2+ afterglow phosphors. Under 975 nm excitation, the hybrids exhibit multicolor emissions from green to white by adjusting laser power and then emit red afterglow light when the 975 nm laser is off. Under synergistic excitation of the blue-green light emitted by Tm/Er microrods, the red afterglow emission not only has a strong initial intensity but also lasts for 3 s. Obvious trichromatic changes from green to white to red can be observed by the naked eye. A pattern printed by the hybrid ink exhibits tricolor emissions by laser adjustment and switch. This proves that upconversion/afterglow hybrids are an excellent candidate for anticounterfeiting applications with high-level security but a simple recognition method.

Micellar Ratiometric Fluorescent Blood pH Probe Based on Triplet-Sensitized Upconversion and Energy-Transfer Behaviors.

The measurement of pH is greatly significant in monitoring physiological and biochemical states. In this work, a novel micellar ratiometric fluorescent probe featuring sophisticated energy-transfer (ET) behaviors with p-nitrophenol (PNP) as the energy acceptor and a triplet-triplet annihilation upconversion (TTA-UC) system as the energy donor was designed. The pH-induced molecular configuration of PNP determined the process for the transfer of energy from TTA-UC to PNP. The introduction of the TTA-UC system enabled probe excitation under a long wavelength and afforded a ratiometric signal for pH detection with excellent reliability over diverse interfering factors. This TTA-UC/ET pH probe demonstrated a high sensitivity to hydronium below nanomolar concentrations and an excellent anti-interference ability in serum samples, which provided a novel significant strategy for rapid and accurate detection of blood pH in vitro.

Ratiometric Fluorescence Detection of Mg2+ Based on Regulating Crown-Ether Modified Annihilators for Triplet-Triplet Annihilation Upconversion.

Detection of magnesium ion has been of great significance considering its critical physiological activities. Herein, we report ratiometric fluorescence detection of Mg2+ with high sensitivity and selectivity based on triplet-triplet annihilation (TTA) upconversion for the first time. Crown-ether functionalized anthracene derivatives were synthesized, which bifunctionally acted as not only annihilators to construct TTA upconversion systems but also the recognition probes for Mg2+ based on the photoinduced electron transfer (PET) mechanism. Their photophysical properties with the absence and presence of Mg2+ were comprehensively studied. It was found that solvents strongly influenced the photophysical properties and Mg2+-responsiveness. TTA upconversion systems with PtOEP as the sensitizer were further established and investigated. It turned out PtOEP/9-AEC in DCM exhibited an excellent linear relationship (R2 = 0.9979) between the intensity ratio (the integrated upconverted luminescence intensity (IUC) over the integrated downshifted phosphorescence intensity (IPL), IUC/IPL) and the concentration of Mg2+ under the excitation of 532 nm with a limit of detection value of 2.52 µM and a high selectivity to Mg2+. This work opened a new perspective of designs and applications of TTA-upconversion-based ratiometric fluorescence for ion detection.

Luminescence Ratiometric Nanothermometry Regulated by Tailoring Annihilators of Triplet-Triplet Annihilation Upconversion Nanomicelles.

Triplet-triplet annihilation (TTA) upconversion is a special non-linear photophysical process that converts low-energy photons into high-energy photons based on sensitizer/annihilator pairs. Here, we constructed a novel luminescence ratiometric nanothermometer based on TTA upconversion nanomicelles by encapsulating sensitizer/annihilator molecules into a temperature-sensitive amphiphilic triblock polymer and obtained good linear relationships between the luminescence ratio (integrated intensity ratio of upconverted luminescence peak to the downshifted phosphorescence peak) and the temperature. We also found chemical modification of annihilators would rule out the interference of the polymer concentration and stereochemical engineering of annihilators would readily regulate the thermal sensitivity.

Highly-efficient red-to-yellow/green upconversion sensitized by phthalocyanine palladium with high triplet energy-level.

Soluble 3,7,11,15-tetra(tert-butyl)phthalocyanine palladium (TBPcPd) and 3,7,11,15-tetra(pentyloxy)phthalocyanine palladium (POPcPd) were synthesized and employed as sensitizers in expectation of achieving red-to-yellow/green upconversion (UC), doped with rubrene (Rub) and 9,10-bis(phenylethynyl)anthracene (BPEA), respectively. Under excitation of a 655 nm diode laser (∼1.5 W cm-2), a maximum red-to-green UC efficiency of 0.07% and a maximum red-to-yellow UC efficiency of 8.03% were obtained and the latter can drive a Si-photodiode to generate obvious photocurrent. The results showed that although a large triplet energy-level difference (ΔE = 3 E sen. - 3 E anni.) of the sensitizer (3 E sen.)/annihilator (3 E anni.) pair helps to improve the upconversion, the sensitizer/annihilator pair with a ΔE value less than zero still works. However, when the ΔE ≤ -0.05 eV, this bicomponent pair is not valid anymore. Thus, a comparison of the ΔE value can predict whether the sensitizer/annihilator pair is useful, which presents a quantitatively evaluated approach for exploring new-type upconversion systems for the first time.

A Stable 2D Zr(IV)-Based Metal-Organic Framework (USTS-7) for Selective Sensing of Cr2O72- in Aqueous Solution.

A novel 2D porous Zr(IV)-based metal-organic framework (USTS-7) was assembled from 2,5-bis[2-(methylthio)ethylthio]terephthalic acid and ZrCl4. USTS-7 retains its stability in water, strong acid, and base; moreover, it is highly luminescent and displays a remarkable selective sensing property toward Cr2O72- in aqueous solution with a very low detection limit.

Recognition and location of motile microorganisms by shape-matching photoluminescence micropatterns.

The typical dimensions of bacterial and microorganism cells match well with the scales at which nanomaterial-based architectures can influence the environment. However, it is one of the most formidable challenges to achieve designed patterns at the microscale for studying microorganisms. Here, we present a method to recognize and locate motile microorganisms at the microscale. The micro-printing strategy via droplet manipulation achieves functional molecule patterning with accurate positions and orientations at the microscale. It is controlled under the interplay between the macroscopic driving forces and the microscopic interfacial dynamics. Photoluminescence patterns have the character of shape matching and uniform light guiding for phototactic microorganisms. The strong attraction among motile microorganisms and photoluminescence patterns prompts microscale artificial selection and location, which will promote the development of self-organized bio-patterning.

Fabricating High-Resolution Metal Pattern with Inkjet Printed Water-Soluble Sacrificial Layer.

The metal pattern plays a crucial role in various optoelectronic devices. However, fabrication of high-resolution metal patterns has serious problems including complicated techniques and high cost. Herein, an inkjet printed water-soluble sacrificial layer was proposed to fabricate a high-resolution metal pattern. The water-soluble sacrificial layer was inkjet printed on a polyethylene glycol terephthalate (PET) surface, and then the printed surface was deposited with a metal layer by evaporating deposition. When the deposited surface was rinsed by water, the metal layer deposited on the water-soluble sacrificial layer could be removed. Various high-resolution metal patterns were prepared, which could be used in electroluminescent displays, strain sensors, and 3D switches. This facile method could be a promising approach for fabricating high-resolution metal patterns.

Fully Printed Geranium-Inspired Encapsulated Arrays for Quantitative Odor Releasing.

Olfactory is an extremely fine way of perception. However, the process of smelling is prone to various interference factors. Further development to enhance the communication desires an odor-releasing strategy, which could quantitatively offer a variety of fragrances. Here, we report a fully printing strategy to heterogeneously integrate odor-containing materials and protective coating films. Inspired from the fragrance-containing drum structure on the geranium leaf, encapsulated arrays are fully printed on the flexible or rigid substrates with more than 20 spices. Quantitative concentrations of odor molecules can be released from the encapsulated arrays after scraping the protective poly(lactic-co-glycolic) acid (PLGA) shells. Importantly, various odor-based arrays are printed on the same flexible substrate, which permits selective releasing and arbitrary mixing of the spices. Effective odor-releasing properties of encapsulated arrays make them promising for food security and anticounterfeiting, investigating olfactory discrimination abilities, and strengthening olfactory communication.

A green solvent for operating highly efficient low-power photon upconversion in air.

d-Limonene, obtained from the rind of citrus fruits, was demonstrated as a green solvent to realize air-stable and highly efficient triplet-triplet annihilation photon upconversion (TTA-UC). This natural low-toxic compound also contributed to noncoherent UC excited by a solar simulator in air, making TTA-UC materials promising candidates in solar energy and other practical applications. The rapid deoxygenating ability of d-limonene was thoroughly investigated. This system demonstrated very good UC performance for a fluid solution under ambient conditions. Besides, other eight types of terpene were also explored to enrich the alternatives for air-stable TTA-UC in protic and aprotic fluidic environments. This work provides a terpene-based protective platform for oxygen-sensitive TTA-UC applications ranging from life science to photonic devices.

Preparation and application of solid-state upconversion materials based on sodium polyacrylate.

By loading a microemulsion containing both sensitizer and emitter into porous sodium polyacrylate (PAAS), a water-absorbent resin (WAR) upconversion (UC) material was fabricated for photocatalysis applications. This WAR UC material showed a highly efficient UC process in the ambient environment owing to its liquid/solid encapsulation structure. In the application measurement, the UC emission from WAR UC materials can excite the catalyst Pt/WO3 to produce hydroxyl radicals, yielding 7-hydroxycoumarin by reacting with coumarin. In another case, since the band gap of ZnCdS matches the energy of UC emission, hole-electron pairs can be obtained under the UC irradiation and capture electrons from rhodamine B, leading to the degradation of rhodamine B. The maximum of the photocatalysis efficiency can be up to 97%. This work solves the oxygen quenching problem by preparing a triplet-triplet annihilation upconversion (TTA-UC) O/W microemulsion and loading it into PAAS WAR, and opens a new avenue to solid-state devices for TTA-UC. The applications of photocatalytic synthesis and photocatalytic degradation lay a foundation for future practical applications for TTA-UC materials.

A stimuli responsive triplet-triplet annihilation upconversion system and its application as a ratiometric sensor for Fe3+ ions.

A ratiometric fluorescent sensor for the detection of Fe3+ ions is achieved based on triplet-triplet annihilation upconversion (TTA-UC) luminescence. A new anthracene derivative (named as DHTPA) is designed and synthesized and reveals similar optical properties to 9,10-diphenylanthracene (DPA) and is used as a stimuli responsive annihilator in a TTA-UC system due to its complexation ability. As a result, the UC emission can be significantly quenched by Fe3+ ions, while the phosphorescence (PL) emission of sensitizer palladium(ii) octaetylporphyrin (PdOEP) remains nearly constant, which makes the PL signal an appropriate internal reference for the UC signal. The UC and ratio signals (I UC/I PL) both reveal a good linear relationship with Fe3+ ion concentration, which for the first time makes the TTA-UC system a perfect ratiometric sensor for Fe3+ ion detection. This sensing method will open a novel avenue to achieve ratiometric sensors in chemical and biological fields.

Programmed Coassembly of One-Dimensional Binary Superstructures by Liquid Soft Confinement.

Precise control of particles co-assembly has attracted great attention for fabricating intricate structures and functional materials. However, achieving precise co-assembly of one-dimensional (1D) binary superstructures remains challenging due to the constrained thermodynamic stability and lack of general strategies to control the 1D ordered arrangement of mixed particles. Here, we propose a facile strategy to achieve programmed co-assembly of 1D binary superstructures by liquid soft confinement without particle modification or external field. It reveals that binary particles undergo stepwise confinement and programmed co-assembly in the gradually shrinking and spatially tunable liquid soft confinement. Through tuning the liquid confined space and particles composition, diverse 1D binary superstructures with precisely controlled periodicity, orientation and symmetry are achieved, which shows generality for various particles of different sizes and materials. This work provides a promising route to refined patterning and manufacturing complex materials.

Rayleigh Instability-Assisted Satellite Droplets Elimination in Inkjet Printing.

Elimination of satellite droplets in inkjet printing has long been desired for high-resolution and precision printing of functional materials and tissues. Generally, the strategy to suppress satellite droplets is to control ink properties, such as viscosity or surface tension, to assist ink filaments in retracting into one drop. However, this strategy brings new restrictions to the ink, such as ink viscosity, surface tension, and concentration. Here, we report an alternative strategy that the satellite droplets are eliminated by enhancing Rayleigh instability of filament at the break point to accelerate pinch-off of the droplet from the nozzle. A superhydrophobic and ultralow adhesive nozzle with cone morphology exhibits the capability to eliminate satellite droplets by cutting the ink filament at breakup point effectively. As a result, the nozzles with different sizes (10-80 µm) are able to print more inks (1 < Z < 38), for which the nozzles are super-ink-phobic and ultralow adhesive, without satellite droplets. The finding presents a new way to remove satellite droplets via designing nozzles with super-ink-phobicity and ultralow adhesion rather than restricting the ink, which has promising applications in printing electronics and biotechnologies.

A general patterning approach by manipulating the evolution of two-dimensional liquid foams.

The evolution of gas-liquid foams has been an attractive topic for more than half a century. However, it remains a challenge to manipulate the evolution of foams, which restricts the development of porous materials with excellent mechanical, thermal, catalytic, electrical or acoustic properties. Here we report a strategy to manipulate the evolution of two-dimensional (2D) liquid foams with a micropatterned surface. We demonstrate that 2D liquid foams can evolve beyond Ostwald ripening (large bubbles always consuming smaller ones). By varying the arrangement of pillars on the surface, we have prepared various patterns of foams in which the size, shape and position of the bubbles can be precisely controlled. Furthermore, these patterned bubbles can serve as a template for the assembly of functional materials, such as nanoparticles and conductive polymers, into desired 2D networks with nanoscale resolution. This methodology provides new insights in controlling curvature-driven evolution and opens a general route for the assembly of functional materials.

Swarm Intelligence-Inspired Spontaneous Fabrication of Optimal Interconnect at the Micro/Nanoscale.

A spontaneous process is demonstrated to assemble nanoparticles into an optimal interconnect, as natural systems spontaneously figure out the shortest path. The optimal interconnect leads to a 65.9% decrease in electromagnetic interference, a 17.1% decrease in delay, and a 24.5% decrease in energy-delay. It will be of great significance for interconnect fabrication of versatile electronic circuits.