Long lifetimes white afterglow in slightly crosslinked polymer systems.

Intrinsic polymer room-temperature phosphorescence (IPRTP) materials have attracted considerable attention for application in flexible electronics, information encryption, lighting displays, and other fields due to their excellent processabilities and luminescence properties. However, achieving multicolor long-lived luminescence, particularly white afterglow, in undoped polymers is challenging. Herein, we propose a strategy of covalently coupling different conjugated chromophores with poly(acrylic acid (AA)-AA-N-succinimide ester) (PAA-NHS) by a simple and rapid one-pot reaction to obtain pure polymers with long-lived RTPs of various colors. Among these polymers, the highest phosphorescence quantum yield of PAPHE reaches 14.7%. Furthermore, the afterglow colors of polymers can be modulated from blue to red by introducing three chromophores into them. Importantly, the acquired polymer TPAP-514 exhibits a white afterglow at room temperature with the chromaticity coordinates (0.33, 0.33) when the ratio of chromophores reaches a suitable value owing to the three-primary-color mechanism. Systematic studies prove that the emission comes from the superposition of different triplet excited states of the three components. Moreover, the potential applications of the obtained polymers in light-emitting diodes and dynamic anti-counterfeiting are explored. The proposed strategy provides a new idea for constructing intrinsic polymers with diverse white-light emission RTPs.

Effective Long Afterglow Amplification Induced by Surface Coordination Interaction.

Long-persistent luminescent (LPL) materials have attracted considerable research interest due to their extensive applications and outstanding afterglow performance. However, the performance of red LPL materials lags behind that of green and blue materials. Therefore, it is crucial to explore novel red LPL materials. This study introduces a straightforward and viable strategy for organic-inorganic hybrids, wherein the organic ligand 1,3,6,8-Tetrakis(4-carboxyphenyl)pyrene (TCPP) is coordinated to the surface of a red persistent phosphor Sr0.75 Ca0.25 S:Eu2+ (R) through a one-step method. TCPP serves as an antenna, facilitating the transfer of absorbed light energy to R via triplet energy transfer (TET). Notably, the initial afterglow intensity and luminance of R increase by twofold and onefold, respectively, and the afterglow duration extends from 9 to 17 min. Furthermore, this study involves the preparation of a highly flexible film by mixing R@TCPP with high-density polyethylene (HDPE) to create a sound-controlled afterglow lamp. This innovative approach holds promising application prospects in flexible large-area luminescence, flexible wearables, and low-vision lighting.

Unique Visualization Growth Process of Long-Lived Room Temperature Phosphorescence in Polymer System.

Recently, embedding organic phosphors into the polyvinyl alcohol (PVA) matrix has emerged as a convenient strategy to obtain efficient long-lived room temperature phosphorescence (RTP) via forming strong intermolecular hydrogen bonds with organic phosphors to minimize nonradiative relaxations. Regrettably, it is discovered that PVA is unable to trigger RTP emission when a novel functional phosphor THBE containing six extended biphenyl formaldehyde arms is doped into PVA matrix. Surprisingly, the excellent long-lived RTP emission can be easily obtained by doping THBE into PVA analogs, poly(vinyl alcohol-co-ethylene) (PVA-co-PE). The unique visualization growth process (i.e., white streak generation) of long-lived RTP is observed by UV light-driven aggregation of functional molecules THBE in PVA-co-PE matrix. The phosphorescent intensity of the luminescent film is enhanced by 55 times, from 729 to 40,785 a.u., and its phosphorescence lifetime is increased by 38 times, from 37.08 to 1415.41 ms. Due to the dynamically reversible RTP performance, as well as the permeability, flexibility, and wrinkle-free properties of the luminescent film, it can be utilized to create cutting-edge information storage devices.

Stepwise taming of triplet excitons via multiple confinements in intrinsic polymers for long-lived room-temperature phosphorescence.

Polymeric materials exhibiting room temperature phosphorescence (RTP) show a promising application potential. However, the conventional ways of preparing such materials are mainly focused on doping, which may suffer from phase separation, poor compatibility, and lack of effective methods to promote intersystem crossing and suppress the nonradiative deactivation rates. Herein, we present an intrinsically polymeric RTP system producing long-lived phosphorescence, high quantum yields and multiple colors by stepwise structural confinement to tame triplet excitons. In this strategy, the performance of the materials is improved in two aspects simultaneously: the phosphorescence lifetime of one polymer (9VA-B) increased more than 4 orders of magnitude, and the maximum phosphorescence quantum yield reached 16.04% in halogen-free polymers. Moreover, crack detection is realized by penetrating steam through the materials exposed to humid surroundings as a special quenching effect, and the information storage is carried out by employing the Morse code and the variations in lifetimes. This study provides a different strategy for constructing intrinsically polymeric RTP materials toward targeted applications.

Enabling Long-Lived Polymeric Room Temperature Phosphorescence Material in Abominable Solvent.

Long-lived polymeric room temperature phosphorescence (RTP) materials have drawn more attention due to their convenient preparation process and equally efficient phosphorescence performance in recent years. As the polymer matrix is sensitive to air and humidity, some non-covalent interactions in the matrix are easily decomposed in water or air, which means that it is difficult for this material to be stored stably for a long time in the atmospheric environment or under harsh conditions. In this work, polymer powder mBPipQ contains aromatic and piperidine rings that are designed and synthesized successfully. Then the polymer is uniformly dispersed into epoxy resin matrix to form long-lived polymeric RTP material with efficient afterglow properties. The stiff backbone structure of mBPip and dense molecular arrangement of epoxy resin provide a rigid environment to stabilize triplet excitons, the RTP performance is greatly enhanced. The lifetime of mBPipQ in epoxy resin is 2 times higher than that of small molecule chromophore in that one. Interestingly, after soaking in strong acid or alkali solution for 10 days, the material can still emit stable and efficient long-lived phosphorescence. It is thanks to the hard matrix after full curing, which can provide a protective layer to prevent external quenchers from interfering with phosphorescence emission. Utilizing the efficient phosphorescence emission and excellent abominable-solvent resistance of this RTP material, multilevel information encryption has been successfully demonstrated. This work broadens the application scope of polymeric RTP materials in harsh environments and provides a new idea for achieving efficient RTP emission.

Long-Lived Dynamic Room Temperature Phosphorescence from Carbon Dots Based Materials.

As a type of room temperature phosphorescence (RTP) material, carbon dots (CDs) always show short lifetime and low phosphorescence efficiency. To counter these disadvantages, several strategies, such as embedding in rigid matrix, introducing of heteroatom, crosslink-enhanced emission, etc., are well developed. Consequently, lots of CDs-based RTP materials are obtained. Doping of CDs into various matrix is the dominant method for preparation of long-lived CDs-based RTP materials so far. The desired CDs@matrix composites always display outstanding RTP performances. Meanwhile, matrix-free CDs and carbonized polymer dots-based RTP materials are also widely developed. Amounts of CDs possessing ultra-long lived, multiple colored, and dynamic RTP emission are successfully obtained. Herein, the recent progress achieved in CDs-based RTP materials as well as the corresponding efficient strategies and emission mechanisms are summarized and reviewed in detail. Due to CDs-based RTP materials possess excellent chemical stability, photostability and low biological toxicity, they exhibit great application potential in the fields of anti-counterfeiting, data encryption, and biological monitoring. The application of the CDs-based RTP materials is also introduced in this review. As a promising functional material, development of long wavelength RTP emitting CDs with long lifetime is still challengeable, especially for the red and near-infrared emitting RTP materials.

A Water-Soluble Core for Manufacturing Hollow Injection-Molded Products.

To manufacture a complicated hollow product without any assembly process, for example, the plastic intake manifold, is difficult by the traditional injection molding method. The fusible-core technique, which uses a low-melting-point alloy as a sacrificial core, was developed to solve this problem; however, the limited selection of resin type and the huge capital investment have caused this technique to spread slowly. In this work, a novel method is established that can produce similar products without the limitation of resin type, as well as a lower-energy-consumption process. The concept of the enveloped core defined by a water-soluble core assembled with a shell is proposed herein; it provides both rigidity and toughness to resist the pressure during the injection molding process. The shape of the enveloped core equals the internal contour of the designated product. An insert molding process was introduced to cover the enveloped core with a skin layer. Cut out the end of the enveloped core and immerse it into a water bath. When the water-soluble core inside the shell is dissolved, the product with a special internal contour is accomplished. A tee-joint is presented to demonstrate how the proposed method can be utilized. The optimal ingredient of the core and processing parameters are determined by the Taguchi method. The result shows that the proposed product is molded successfully when the compressive strength of the core is larger than 2 MPa. In addition, the eccentricity measurement of internal contour of the optimal sample exhibits a 56% improvement, and the required time for the core removal is less than 154 s.

Poly(arylene piperidine) Quaternary Ammonium Salts Promoting Stable Long-Lived Room-Temperature Phosphorescence in Aqueous Environment.

Room-temperature phosphorescence (RTP) materials have garnered considerable research attention owing to their excellent luminescence properties and potential application prospects in anti-counterfeiting, information storage, and optoelectronics. However, several RTP systems are extremely sensitive to humidity, and consequently, the realization of long-lived RTP in water remains a formidable challenge. Herein, a feasible and effective strategy is presented to achieve long-lived polymeric RTP systems, even in an aqueous environment, through doping of synthesized polymeric phosphor PBHDB into a poly(methyl methacrylate) (PMMA) matrix. Compared to the precursor polymer PBN and organic molecule HDBP, a more rigid polymer microenvironment and electrostatic interaction are formed between the PMMA matrix and polymer PBHDB, which effectively reduce the nonradiative decay rate of triplet excitons and dramatically increase the phosphorescence intensity. Specifically, the phosphorescence lifetime of the PBHDB@PMMA film (1258.62 ms) is much longer than those of PBN@PMMA (674.20 ms) and HDBP@PMMA (1.06 ms). Most importantly, a bright-green afterglow can be observed after soaking the PBHDB@PMMA film in water for more than a month. The excellent water resistance and reversible response properties endow these systems with promising potential for dynamic information encryption even in water.

Full-Color Long-Lived Room Temperature Phosphorescence in Aqueous Environment.

Long-lived room temperature phosphorescence (RTP) materials are widely utilized in the field of biological and chemical sensing, due to their unique characteristics of long-lived luminescence and no background autofluorescence. However, the realization of full-color RTP in aqueous solution still remains a great challenge. Herein, a feasible strategy for achieving high stability and full-color RTP of carbon dots (CDs)-based composite materials in aqueous environment is reported by constructing a rigid hydrogen bonds' network. The obtained m,p-CDs@CA composite materials exhibit deep-blue RTP with phosphorescence quantum yield of 23.2% and lifetime of 1.74 s, and the afterglow can last for over 12 s. More importantly, the m,p-CDs@CA composite materials are desirable in the detection of biomarkers, because of excellent stability, dispersion, and long-lived RTP properties. The m,p-CDs@CA suspension also displays excellent sensitivity, and a limitation of detection as low as 5.61 and 550 nm for biomarkers 5-hydroxyindole-3-acetic acid (HIAA) and serotonin (5-hydroxytryptamine, HT), respectively. Meanwhile, the sensing performance exhibits excellent selectivity even in the presence of other competitive species in blood plasma and urine. With superior selectivity, the long-lived phosphorescence probe based on m,p-CDs@CA suspension can be as an effective biomarker for carcinoid identification, which has potential application in clinical analysis.

Core-shell Pd-P@Pt-Ni nanoparticles with enhanced activity and durability as anode electrocatalyst for methanol oxidation reaction.

Pd-P@Pt-Ni core-shell nanoparticles, which consisted of a Pd-P alloy as a core and Pt-Ni thin layer as a shell, were explored as electrocatalysts for methanol oxidation reaction. The crystallographic information and the electronic properties were fully investigated by X-ray diffraction and X-ray photoelectron spectroscopy. In the methanol electrooxidation reaction, the particles showed high catalytic activity and strong resistance to the poisoning carbonaceous species in comparison with those of commercial Pt/C and the as-prepared Pt/C catalysts. The excellent durability was demonstrated by electrochemically active surface area loss and chronoamperometric measurements. These results would be due to the enhanced catalytic properties of Pt by the double synergistic effects from the core part and the nickel species in the shell part.

Hollow terbium metal-organic-framework spheres: preparation and their performance in Fe3+ detection.

Hollow metal-organic framework (MOF) micro/nanostructures have been attracting a great amount of research interest in recent years. However, the synthesis of hollow metal-organic frameworks (MOFs) is a great challenge. In this paper, by using 1,3,5-benzenetricarboxylic acid (H3BTC) as the organic ligand and 2,5-thiophenedicarboxylic acid (H2TDC) as the competitive ligand and protective agent, hollow terbium MOFs (Tb-MOFs) spheres were synthesized by a one-pot solvothermal method. By comparing the morphology of Tb-MOFs in the presence and absence of H2TDC, it is found that H2TDC plays a key role in the formation of the hollow spherical structure. Single crystal analyses and element analysis confirm that H2TDC is not involved in the coordination with Tb3+. Interestingly, Tb-MOFs can be used as the luminescent probes for Fe3+ recognition in aqueous and N,N-dimethylformamide (DMF) solutions. In aqueous solution, the quenching constant (K SV) is 5.8 × 10-4 M-1, and the limit of detection (LOD) is 2.05 µM. In DMF, the K SV and LOD are 9.5 × 10-4 M-1 and 0.80 µM, respectively. The sensing mechanism is that the excitation energy absorption of Fe3+ ions reduces the energy transfer efficiency from the ligand to Tb3+ ions.

Four-in-One Stimulus-Responsive Long-Lived Luminescent Systems Based on Pyrene-Doped Amorphous Polymers.

Materials exhibiting ultralong luminescent lifetime show promising applications in the fields of information encryption, sensing, and bioimaging. Herein, we present a low-cost and general strategy to achieve stimulus-responsive ultralong organic phosphorescence (UOP) based on pyrene chromophores doped into polymer matrices. The UOP of the resulted systems presents radiation-, concentration-, time-, and excitation-dependent characteristics. The UOP color can be turned from blue to red by changing the excitation wavelength or the concentration of chromophores. Experimental results prove that these characteristics are attributed to the consumption of triplet oxygen and the different aggregation states of chromophores in the polymer matrices. Finally, we demonstrate that these systems could be applied for multilevel information encryption. This work would promote further development of multi-responsive long-lived luminescent materials.

Long-Lived Organic Room-Temperature Phosphorescence from Amorphous Polymer Systems.

Long-lived organic room-temperature phosphorescence (RTP) materials have recently drawn extensive attention because of their promising applications in information security, biological imaging, optoelectronic devices, and intelligent sensors. In contrast to conventional fluorescence, the RTP phenomenon originates from the slow radiative transition of triplet excitons. Thus, enhancing the intersystem crossing (ISC) rate from the lowest excited singlet state (S1) to the excited triplet state and suppressing the nonradiative relaxation channels of the lowest excited triplet state (T1) are reasonable methods for realizing highly efficient RTP in purely organic materials. Over the past few decades, many strategies have been designed on the basis of the above two crucial factors. The introduction of heavy atoms, aromatic carbonyl groups, and other heteroatoms with abundant lone-pair electrons has been demonstrated to strengthen the spin-orbit coupling, thereby successfully facilitating the ISC process. Furthermore, the rigid environment is commonly constructed through crystal engineering to restrict intramolecular motions and intermolecular collisions to decrease excited-state energy dissipation. However, most crystal-based organic RTP materials suffer from poor processability, flexibility, and reproducibility, becoming a thorny obstacle to their practical application.Amorphous organic polymers with long-lived RTP characteristics are more competitive in materials science. The intertwined structures and long chains of polymers not only ensure the rigid environment with multiple interactions but also protect triplet excitons from the surroundings, which are conducive to realizing ultralong and bright RTP emission. Exploring the fabrication strategies, intrinsic mechanisms, and practical applications of organic long-lived RTP polymers is highly desirable but remains a formidable challenge. In particular, intelligent organic RTP polymer systems that are capable of dynamically responding to external stimuli (e.g., light, temperature, oxygen, and humidity) have been rarely reported. To develop multifunctional RTP materials and expand their potential applications, a great amount of effort has been expended.This Account gives a summary of the significant advances in amorphous organic RTP polymer systems, especially smart stimulus-responsive ones, focusing on the construction of a rigid environment to suppress nonradiative deactivation by abundant inter/intramolecular interactions. The typical interactions in RTP polymer systems mainly include hydrogen bonding, ionic bonding, and covalent bonding, which can change the molecular electronic structures and affect the energy dissipation channels of the excited states. An in-depth understanding of intrinsic mechanisms and an extensive exploration of potential applications for excitation-dependent color-tunable, ultraviolet (UV) irradiation-activated, temperature-dependent, water-responsive, and circularly polarized RTP polymer systems are distinctly illustrated in this Account. Furthermore, we propose some detailed perspectives in terms of materials design, mechanism exploration, and promising application potential with the hope to provide helpful guidance for the future development of amorphous organic RTP polymers.

Cross-Linked Polyphosphazene Nanospheres Boosting Long-Lived Organic Room-Temperature Phosphorescence.

Long-lived organic room-temperature phosphorescence (RTP) has sparked intense explorations, owing to the outstanding optical performance and exceptional applications. Because triplet excitons in organic RTP experience multifarious relaxation processes resulting from their high sensitivity, spin multiplicity, inevitable nonradiative decay, and external quenchers, boosting RTP performance by the modulated triplet-exciton behavior is challenging. Herein, we report that cross-linked polyphosphazene nanospheres can effectively promote long-lived organic RTP. Through molecular engineering, multiple carbonyl groups (C═O), heteroatoms (N and P), and heavy atoms (Cl) are introduced into the polyphosphazene nanospheres, largely strengthening the spin-orbit coupling constant by recalibrating the electronic configurations between singlet (Sn) and triplet (Tn) excitons. In order to further suppress nonradiative decay and avoid quenching under ambient conditions, polyphosphazene nanospheres are encapsulated with poly(vinyl alcohol) matrix, thus synchronously prompting phosphorescence lifetime (173 ms longer), phosphorescence efficiency (∼12-fold higher), afterglow duration time (more than 20 s), and afterglow absolute luminance (∼19-fold higher) as compared with the 2,3,6,7,10,11-hexahydroxytriphenylene precursor. By measuring the emission intensity of the phosphorescence, an effective probe based on the nanospheres is developed for visible, quantitative, and expeditious detection of volatile organic compounds. More significantly, the obtained films show high selectivity and robustness for anisole detection (7.1 × 10-4 mol L-1). This work not only demonstrates a way toward boosting the efficiency of RTP materials but also provides a new avenue to apply RTP materials in feasible detection applications.

Long-Lived Room Temperature Phosphorescence Crystals with Green Light Excitation.

Long-lived room temperature phosphorescence (RTP) materials are promising for applications in various fields including security information, medical diagnostics, and molecular imaging because of their unique optical properties. Previous RTP materials are mainly excited by ultraviolet light, while synthesizing long-lived RTP materials with visible-light-excitation remains a challenge. In particular, long-lived RTP materials that can be excited by green light are rare. Herein, a feasible and concise chemical strategy for constructing hydrogen-bonded frameworks in an aqueous environment is developed to fabricate large-size, green-light-excited, and excitation-dependent long-lived RTP carbon dot crystals (m,p/CDs-ME). The RTP performance of the crystals exhibits strong excitation wavelength dependence, leading to a full range of visible-light tuning from blue to red. Importantly, the maximum excitation wavelength of the RTP crystals is around 500 nm, thus successfully realizing green light excitation. m,p/CDs-ME presents long-lived phosphorescence (130 ms) under 500 nm excitation in aqueous solution, making it highly suitable for dopamine detection. This work not only provides a general guideline for the development of large size long-lived RTP crystals but also extends the operation scope of long-lived RTP materials in the detection of biomarkers by visible light excitation.

Jasmonic acid biosynthetic genes TgLOX4 and TgLOX5 are involved in daughter bulb development in tulip (Tulipa gesneriana).

The tulip bulbs are modified underground stems which originate from axillary meristems of mother bulb scales. Hormones including jasmonic acids (JAs) play key roles in regulating tulip bulb development. Here, we compared variations of daughter bulb development through transcriptomic profiling analysis and characterized the functions of JA biosynthesis related genes during daughter bulb enlargement. The results showed that tulip varieties exhibited contrasting bulb size variations. Transcriptomic analyses revealed that genes involved in plant hormones and development were significantly changed following tulip bulb growth, including two lipoxygenase genes TgLOX4 and TgLOX5. Ectopic overexpression of TgLOX4 and TgLOX5 in Arabidopsis enhanced endogenous JA content, improved plant growth and increased lateral root numbers. Silencing of these two genes in tulip repressed the growth of daughter bulbs. Furthermore, exogenous JA treatment promoted tulip bulb growth, whereas JA biosynthesis inhibitor sodium diethyldithiocarbamate (DIECA) inhibited this process. This study offers supporting evidence for the involvement of tulip TgLOX4 and TgLOX5 in the regulation of daughter bulb growth and development.

Large-Area, Flexible, Transparent, and Long-Lived Polymer-Based Phosphorescence Films.

Polymer-based room-temperature phosphorescence (RTP) materials with high flexibility and large-area producibility are highly promising for applications in organic electronics. However, achieving such photophysical materials is challenging because of difficulties in populating and stabilizing susceptible triplet excited states at room temperature. Herein large-area, flexible, transparent, and long-lived RTP systems prepared by doping rationally selected organic chromophores in a poly(vinyl alcohol) (PVA) matrix were realized through a hydrogen-bonding and coassembly strategy. In particular, the 3,6-diphenyl-9H-carbazole (DPCz)-doped PVA film shows long-lived phosphorescence emission (up to 2044.86 ms) and a remarkable duration of afterglow (over 20 s) under ambient conditions. Meanwhile, the 7H-dibenzo[c,g]carbazole (DBCz)-doped PVA film exhibits high absolute luminance of 158.4 mcd m2 after the ultraviolet excitation source is removed. The RTP results not only from suppressing the nonradiative decay by abundant hydrogen-bonding interactions in the PVA matrix but also from minimizing the energy gap (ΔEST) between the singlet state and the triplet state through the coassembly effect. On account of the outstanding mechanical properties and the afterglow performance of these RTP materials, they were applied in the fabrication of flexible 3D objects with repeatable folding and curling properties. Importantly, the multichannel afterglow light-emitting diode arrays were established under ambient conditions. The present long-lived phosphorescent systems demonstrate a bright opportunity for the production of large-area, flexible, and transparent emitting materials.

Ultrastable Tb-Organic Framework as a Selective Sensor of Phenylglyoxylic Acid in Urine.

Industrial pollution and harmful chemicals seriously affect environment and human health. Styrene is a common air toxicant with widespread exposure sources, including smoking, automobile exhaust, and plastic pollutants. Phenylglyoxylic acid (PGA) is a typical biomarker for exposed styrene. Therefore, it is crucial to quickly identify and quantitatively detect PGA. Herein, an ultrastable terbium metal-organic framework (Tb-MOF 1) was developed, and the luminescence film (1/PLA) consisting of polylactic acid (PLA) and 1 was fabricated as a sensor for rapid detection of PGA. The sensor possesses the advantages of efficient detection [limit of detection (LOD) is 1.05 × 10-4 mg/mL] and rapid response speed (less than 10 s) for PGA in urine. Furthermore, this sensor exhibits high stability, outstanding anti-interference ability, and excellent recyclability. Based on this film technology, a paper-based probe was then developed for portable and convenient detection. The probe could easily distinguish different concentrations of PGA under the naked eye toward practical sensing applications. Meanwhile, photoinduced electron transfer was demonstrated to be responsible for the luminescence sensing. Hence, this study indicates that Tb-MOF is a promising material to detect PGA for evaluating the effect of styrene on the body.

Ultraviolet irradiation-responsive dynamic ultralong organic phosphorescence in polymeric systems.

Room temperature phosphorescence (RTP) has drawn extensive attention in recent years. Efficient stimulus-responsive phosphorescent organic materials are attractive, but are extremely rare because of unclear design principles and intrinsically spin-forbidden intersystem crossing. Herein, we present a feasible and facile strategy to achieve ultraviolet irradiation-responsive ultralong RTP (IRRTP) of some simple organic phosphors by doping into amorphous poly(vinyl alcohol) matrix. In addition to the observed green and yellow afterglow emission with distinct irradiation-enhanced phosphorescence, the phosphorescence lifetime can be tuned by varying the irradiation period of 254 nm light. Significantly, the dynamic phosphorescence lifetime could be increased 14.3 folds from 58.03 ms to 828.81 ms in one of the obtained hybrid films after irradiation for 45 min under ambient conditions. As such, the application in polychromatic screen printing and multilevel information encryption is demonstrated. The extraordinary IRRTP in the amorphous state endows these systems with a highly promising potential for smart flexible luminescent materials and sensors with dynamically controlled phosphorescence.

Lanthanide Metal-Organic Framework-Based Fluorescent Sensor Arrays to Discriminate and Quantify Ingredients of Natural Medicine.

The discrimination and quantification of the ingredients from natural medicines are a challenging issue due to their complicated and various structures. Metal-organic frameworks (MOFs) have shown great promise in sensing applications. Here, we report a fluorescent sensor array for rapid identification of some natural compounds using a sensor array composed of four kinds of lanthanide (Eu3+ and Tb3+) fluorescent MOFs (Ln-MOFs), which have diversified fluorescent responses to 26 active/toxic compounds including 12 saponins, 7 flavonoids, 3 stilbenes, and 4 anthraquinones. The fluorescence of the Ln-MOFs after reaction with the compounds was summarized as datasets and processed by principle component analysis (PCA) and hierarchical cluster analysis (HCA) methods. The corresponding responses of the 4 types of compounds are well separated on 2D/3D PCA score plots and HCA dendrograms. We have also tested typical blind samples by concentration-dependent PCA, and an accuracy of 100% was obtained. In addition, the response mechanisms of the Ln-MOFs to the compounds were also studied. Compared with traditional methods using liquid chromatography-mass spectrometry, the developed fluorescent sensor array provides a more efficient and economic strategy to discriminate various active/toxic ingredients in natural medicine.