Interfacing Ag2S Nanoparticles and MoS2 Nanosheets on Polypyrrole Nanotubes with Enhanced Catalytic Performance.

The tubular architecture with multiple components can bring synergistic effects to improve the enzyme-like activity of molybdenum-based nanomaterials. Here, a facile polypyrrole (PPy)-protected hydrothermal sulfidation process was implemented to engineer MoS2/Ag2S heterointerfaces encapsulated in one-dimensional (1D) PPy nanotubes with MoO3@Ag nanorods as the self-sacrificing precursor. Notably, the sulfidation treatment led to the generation of MoS2 nanosheets (NSs) and Ag2S nanoparticles (NPs) and the creation of a tubular structure with a "kill three birds with one stone" role. The Ag2S/MoS2@PPy nanotubes showed the synergistic combined effects of Ag2S NPs, MoS2 NSs, and the 1D tube-like nanostructure. Based on the synergistic effects from these multiple components and the tubular structure, Ag2S/MoS2@PPy nanocomposites were used as a colorimetric sensing platform for detecting H2O2. Moreover, the reduction of 4-nitrophenol (4-NP) revealed excellent catalytic activity in the presence of NaBH4 and Ag2S/MoS2@PPy nanocomposites. This work highlights the effects of MoS2/Ag2S heterointerfaces and the hierarchical tubular structure in catalysis, thereby providing a new avenue for reducing 4-NP and the enzyme-like catalytic field.

Co, Fe Dual-Doped MoS2 Nanosheets on Polypyrrole Microtubes as Effective Peroxidase Mimics for Glutathione Sensing.

Heteroatom doping is considered an effective way to enhance the catalytic activity of MoS2 nanosheets (NSs). In the paper, dual-metal doping was proposed to incorporate Fe and Co into hierarchical MoS2 ultrathin NSs, which grew directly on polypyrrole microtubes (Fe, Co-MoS2@PPy), for the enhanced enzyme-like catalytic reaction. The particular hollow tubular structure realized effective electron transfer. The doped Fe and Co tuned the electronic architecture of the MoS2 NSs to enhance the enzyme-like catalytic activity. The abundant exposed void spaces facilitated ion diffusion/penetration between the PPy interlayer and Fe-Co doped MoS2 shell, leading to heterostructured synergistic effects. Therefore, the synthesized Fe and Co-MoS2@PPy composites showed remarkable catalytic activity. The high catalytic efficiency of Fe and Co-MoS2@PPy was confirmed with the reaction of tetramethylbenzidine (TMB) and H2O2 for visible detection. The blue color disappeared after adding glutathione (GSH). Thus, this procedure was used as a convenient way to detect GSH with a detection limit of 0.76 µM. The dual-metal-doped strategy was confirmed to improve the performance of MoS2 nanocomposites and could be used as a promising matrix for other applications, such as electrochemical energy conversion, medical diagnosis, and others.

Carbon dots with enhanced red emission for ratiometric sensing and encryption applications.

The excitation-dependent emission properties of carbon dots (Cdots) are extensively reported, but their red emission is often weak, limiting their wider application. Here we introduce ethidium bromide, as a functional precursor with red emission, to enhance the red emission for Cdots, with comparable intensity at a broad wavelength range to multi-emission Cdots (M-Cdots). We found that Cdots prepared with ethidium bromide/ethylenediamine exhibited strong blue and red emission at 440 and 615 nm, with optimal excitation at 360 and 470 nm as M-Cdots, respectively, but the Cdots from single ethidium bromide (EB-Cdots) possessed weak red emission. M-Cdots exhibited a broad absorption band at 478 nm, but a band blue-shifted to 425 nm was observed for EB-Cdots, while no absorption was observed at 478-425 nm for the Cdots prepared with citric acid and ethylenediamine. Thus, we proposed that C=O and C=N formed a π-conjugation structure as the absorption band at 478 nm for the red emission of M-Cdots, as also confirmed with the excitation at 470 nm. Moreover, the π-conjugation structure is fragile and sensitive to harsh conditions, so red emission was difficult to observe for the Cdots prepared with citric acid/ethylenediamine or single ethidium bromide. M-Cdots possess two centers for blue and red emission with different structures. The dual emission was therefore used for ratiometric sensing with dichromate (Cr2O72-) and formaldehyde (HCHO) as the targets using the intensity ratio of the emissions at 615 and 440 nm. Due to the comparable intensity at a broad wavelength range, we designed encryption codes with five excitations at 360, 400, 420, 450, and 470 nm as the inputs, and the emission colors were used for information decoding. Thus, we determined why red emission was difficult to realize for Cdots, and our results could motivate the design of red-emission Cdots for extensive applications.

General Approach to Construct C-C Single Bond-Linked Covalent Organic Frameworks.

C-C single bond-linked covalent organic frameworks (CSBL-COFs) are extremely needed because of their excellent stabilities and potential applications in harsh conditions. However, strategies to generate CSBL-COFs are limited to the acetylenic self-homocoupling Glaser-Hay reaction or post-synthetic reduction of vinylene-based COFs. Exploring new strategies to expand the realm of CSBL-COFs is urgently needed but extremely challenging. To address the synthetic challenges, we for the first time developed a general approach via the reaction between aromatic aldehydes and active methyl group-involving monomers with enhanced acidity, which realized the successful construction of a series of CSBL-COFs. As expected, the obtained CSBL-COFs exhibited outstanding chemical stability, which can stabilize in 6 M NaOH, 3 M HCl, boiling water, and 100 mg/mL NaBH4 for at least 3 days. It is important to mention that CSBL-COFs possess a large amount of ionic sites distributed throughout the networks; gentle shaking allowed our COFs to easily self-disperse as nanoparticles and suspend in water for at least 12 h without reprecipitating. As far as we know, such self-dispersed COFs with high water dispersity are rare to date, and few examples are mainly limited to the guanidinium- and pseudorotaxane-based COFs. Our work thus developed a family of self-dispersed COFs for potential applications in different sorts of fields. Our contribution would thus pave a new avenue for constructing a broader class of CSBL-COFs for their wide applications in various fields.

Reactive Template-Engaged Synthesis of NiSx/MoS2 Nanosheets Decorated on Hollow and Porous Carbon Microtubes with Optimal Electronic Modulation toward High-Performance Enzyme-like Performance.

As a promising cost-effective nanozyme, MoS2 nanosheets (NSs) have been considered as a good candidate for the enzyme-like catalysis. However, their catalytic activity is still restricted by the insufficient active sites and poor conductivity, and thus, the comprehensive performances are still unsatisfactory. To address these issues, herein, we design and fabricate an intelligent tubular nanostructure of hierarchical hollow nanotubes, which are assembled by NiSx/MoS2 NSs encapsulated into N-doped carbon microtubes (NiSx/MoS2@NCMTs). The N-doped carbon microtubes (NCMTs) serve as a conductive skeleton, integrating with NiSx/MoS2 NSs and ensuring their well-distribution, thereby maximally exposing more active sites. Additionally, the tube-like structure is favorable for increasing the mass transfusion to ensure their excellent catalytic performance. Profiting from their component and structural advantages, the obtained NiSx/MoS2@NCMTs exhibit a surprisingly enhanced enzyme-like activity. Based on these, a facile colorimetric sensing platform to detect H2O2 and GSH has been developed. This proposed approach can be expected to synthesize a series of tubular heterostructured MoS2-based composites, which will be widely applied in catalysis, energy storage, disease diagnosis, etc.

Organic Electrochemical Transistor Based on Hydrophobic Polymer Tuned by Ionic Gels.

Hydrophobic conjugated polymers have poor ionic transport property, so hydrophilic side chains are often grafted for their application as organic electrochemical transistors (OECTs). However, this modification lowers their charge transport ability. Here, an ionic gel interfacial layer is applied to improve the ionic transport while retaining the charge transport ability of the polymers. By using the ionic gels comprising gel matrix and ionic liquids as the interfacial layers, the hydrophobic polymer achieves the OECT feature with high transconductance, low threshold voltage, high current on/off ratio, short switching time, and high operational stability. The working mechanism is also revealed. Moreover, the OECT performance can be tuned by varying the types and ratios of ionic gels. With the proposed ionic gel strategy, OECTs can be effectively realized with hydrophobic conjugated polymers.

Design and Multiple Applications of Mixed-Ligand Metal-Organic Frameworks with Dual Emission.

Herein, we revealed the factors that affect the emission in mixed-ligand metal-organic frameworks (MOFs) with the combination of terephthalic acid (BDC), 2-aminoterephthalic acid (BDC-NH2), and 2,5-dihydroxylterephthalic acid [BDC-(OH)2] as models. The -NH2 and -(OH)2 groups change the π-conjugation and luminescence behaviors than BDC, so the ligands show different optical behaviors. The Zn2+ ion with a 3d10 full electronic structure shows little effect on the emission of the ligand and is selected as the metal node. We found that the emission of BDC is weak and incompatible to that of BDC-NH2, so only the emission of BDC-NH2 was observed in the BDC/BDC-NH2-MOF. Crosstalk occurs between the emissions from BDC and BDC-(OH)2 for the single emission from BDC/BDC-(OH)2-MOFs, even different ratios are selected. The MOFs prepared with BDC-NH2 and BDC-(OH)2 show dual emission at 450 and 550 nm, while the relative intensity was easily tuned with the ligand ratio and excitation wavelength. Thus, abundant optical behaviors and extensive applications were realized, including but not limited to (1) dual emission from single MOFs, (2) tunable color from blue to yellow with the excitation from 290 to 370 nm for information encryption and decryption, (3) white emission obtained under an excitation of 330 nm, and (4) response of -NH2 groups to HCHO and Fe3+ ions for ratiometric fluorescence sensing and visual detection. This work revealed the factors that affect the emission in mixed-ligand MOFs, studied their optical behaviors, and realized different applications with single MOFs.

Multi-Emission from Single Metal-Organic Frameworks under Single Excitation.

Multi-emission materials have come to prominent attention ascribed to their extended applications other than single-emission ones. General and robust design strategies of a single matrix with multi-emission under single excitation are urgently required. Metal-organic frameworks (MOFs) are porous materials prepared with organic ligands and metal nodes. The variety of metal nodes and ligands makes MOFs with great superiority as multi-emission matrices. Guest species encapsulated into the channels or pores of MOFs are the additional emission sites for multi-emission. In this review, multi-emission MOFs according to the different excitation sites are summarized and classified. The emission mechanisms are discussed, such as antenna effect, excited-state intramolecular proton transfer (ESIPT) and tautomerism for dual-emission. The factors that affect the emissions are revealed, including ligand-metal energy transfer and host-guest interaction, etc. Multi-emission MOFs could be predictably designed and prepared, once the emissive factors are controlled rationally in combination with the different multi-emission mechanisms. Correspondingly, new and practical applications are realized, including but not limited to ratiometric/multi-target sensing and bioimaging, white light-emitting diodes, and anti-counterfeiting. The design strategies of multi-emission MOFs and their extensive applications are reviewed. The results will shed light on other multi-emission systems to develop the structure-derived functionality and applications.

In Situ Construction of Co-MoS2/Pd Nanosheets on Polypyrrole-Derived Nitrogen-Doped Carbon Microtubes as Multifunctional Catalysts with Enhanced Catalytic Performance.

The structural design of multiple functional components could integrate synergistic effects to enhance the catalytic performance of MoS2-based composites for catalytic applications. Herein, one-dimensional (1D) Co-MoS2/Pd@NCMTs composites were designed to prepare Co-doped MoS2/Pd nanosheets (NSs) on N-doped carbon microtubes (NCMTs) from tubular polypyrrole (PPy) as multifunctional catalysts. The Co-MoS2/Pd@NCMTs composites integrated the synergistic effects of Co-doping, a 1D tubular structure, and noble-metal Pd decoration. Thus, a higher catalytic activity was observed in 4-nitrophenol (4-NP) reduction and peroxidase-like catalysis than other components, such as MoS2, MoS2@NCMTs, and Co-MoS2@NCMTs. Remarkably, the results indicated that the dissolution, diffusion, and redistribution led to the dissolution of MoO3@ZIF-67 cores and generation of Co-doped MoS2 NSs. Benefiting from the synergistic effect from these components, Co-MoS2/Pd@NCMTs were considered as a facile colorimetric sensing platform for detecting tannic acid. Moreover, outstanding performance was realized in the reduction of 4-NP with the composites. Thus, we provide a simple synthetic strategy for simultaneously integrating electronic engineering and structural advantages to develop an efficient MoS2-based multifunctional catalyst.

Dual-Ligand Lanthanide Metal-Organic Framework for Sensitive Ratiometric Fluorescence Detection of Hypochlorous Acid.

Sensitivity, selectivity, visible detection, and rapid response are the main concerns for an analytical method. Herein, we reported a metal-organic framework (MOF)-based ratiometric fluorescence detection strategy for hypochlorous acid (HClO). The MOF was prepared with dual ligands, 2-aminoterephthalic acid (BDC-NH2) and dipicolinic acid (DPA) and Eu3+ ions as a metal node, denoted as Eu-BDC-NH2/DPA. The dual-ligand strategy realized the dual emission for ratiometric sensing and visual detection, adjusted the size and morphology of MOFs to obtain a good dispersion for a rapid response, and provided an amino group for the special recognition of HClO. Thus, the MOF exhibited a dual emission derived from BDC-NH2 and Eu3+ ions at 433 and 621 nm, respectively, under a single excitation at 270 nm. A hydrogen bond forms between an -NH2 group and HClO to weaken the blue fluorescence at 433 nm, while the antenna effect emission from Eu3+ ions kept stable, so ratiometric sensing was realized with an easy-to-differentiate color change for visible detection. The ratiometric sensing showed a self-calibration effect and reduced the background. Thus, the high sensitivity, visual detection, low detection limit (37 nM), and short response time (within 20 s) for the detection of HClO were realized with the MOF as a probe. The analysis of real samples demonstrated the practical application of the MOF for HClO. The introduction of mixed ligands is an effective strategy to regulate the emission behaviors of MOFs for the improved analytical performance.

Construction of NaYF4 Library for Morphology-Controlled Multimodality Applications.

Morphology and size of the nanoparticles are highly related to the properties; establishing a library to summarize the relationship between the morphology/size and property is very helpful for associated applications. However, the NaYF4 library and thus the correlation between the morphology and property are still absent. Here NaYF4 library is presented and their morphologies and structures are illustrated at atomic scale for the first time. How about the crystal formation affects the morphology is further used to guide the property. Through rational doping, upconversion luminescence, magnetic resonance (MR) and computed tomography are investigated with the nanoprisms, nanoflowers, and nanoplates as models to reveal the effect of the size and morphology. The difference of the properties provides strong evidence on the importance of the library. In particular, the "imperfect structure" of nanoflower is observed on atomic scale and enhances the MR response. The different upconversion intensity ratio for the emissions at 475 and 693 nm is observed from doped NaYF4 with different morphology. Thus, controllable fabrication of NaYF4 with desired morphology is indispensable to achieve the optimal properties as the guidance on how to choose matrix from the library to meet the specific applications.

Metal-Organic Frameworks with Multiple Luminescence Emissions: Designs and Applications.

Emissive species are powerful for luminescent detection with high sensitivity and simple procedure and for light-emitting diode (LED) lighting because of their high efficiency, long lifetime, and low energy consumption. Here we propose the concept of multiple luminescence emissions from a single matrix or species under single-wavelength excitation. Multiemission not only realizes the high sensitivity of luminescence sensing but also possesses the capacity of self-reference for environment-free interferences. The color change is also convenient for visible detection. In multiemission species, every emissive center responds to a specific analyte to improve the efficiency for multiple-target detection. Multiemission also extends the applications to anticounterfeiting, colorful LEDs, and information storage. To date, it is still challenging to combine more than one type of emissive center in a single matrix or species. Obtaining multiemission under single-wavelength excitation also needs exquisite design. Metal-organic frameworks (MOFs) are porous hybrid assemblies prepared with metal ions and organic ligands. Metal nodes and ligands with large π-conjugated systems have the potential for the construction of luminescent MOFs. Abundant and diverse precursors provide the possibility to prepare MOFs with multiple luminescence emissions. The pores or channels of MOFs also act as hosts to encapsulate luminescent guest species as additional emissive sites. In this Account, we propose the concept of multiple-luminescence MOFs (ML-MOFs) and summarize the recent research progress on their designs, constructions, and applications reported by our group and others. ML-MOFs are MOFs that possess more than one emissive center under single-wavelength excitation. Six different kinds of construction strategies of ML-MOFs are introduced: (1) multiemission from both metal nodes and ligands in single MOFs; (2) use of mixed-metal nodes as multiemission centers in single MOFs; (3) combination of different emissive MOFs as a whole to achieve multiemission application; (4) host-guest emissions from emissive MOFs after encapsulation of luminescent guest species; (5) organization of different emissive ligands in a single MOF for multiemission; and (6) use of single ligands exhibiting dual emission to prepare ML-MOFs. We also discuss the mechanisms that realize multiple emissions from MOFs under single-wavelength excitation, such as the antenna effect and excited-state intramolecular proton transfer. The applications of ratiometric sensing, LED lighting, anticounterfeiting, and information storage are summarized. With this Account, we hope to spark new ideas and to inspire new endeavors in the design and construction of ML-MOFs, especially with postsynthetic techniques such as postsynthetic modification, postsynthetic exchange, and postsynthetic deprotection, to promote the applications of MOFs in sensing, lighting, information storage, and others.

Enhancement of Solar-Driven Photocatalytic Activity of BiOI Nanosheets through Predominant Exposed High Energy Facets and Vacancy Engineering.

The increasing application of exposed high energy facet is an effective strategy to improve the photocatalytic performance of photocatalysts because the vacancies are beneficial to photocatalytic reaction. Vacancy dominates numerous distinct properties of semiconductor materials and thus plays a conclusive role in the photocatalysis applications. In this work, two kinds of BiOI nanomaterials with different vacancies are synthesized via a facile solvothermal method. The positron annihilation analysis shows that the thinner BiOI nanosheets possess larger-sized vacancy than BiOI nanoplates. Thus, BiOI nanosheets show the enhanced separation efficiency of electron-hole pairs and adsorption ability for contaminants under visible light. The results are also validated with the first-principle computation. Therefore, higher photocatalytic activity to the photodegradation of tetracycline is observed from the nanosheets than that obtained from BiOI nanoplates. This work not only arouses attention to vacancies, but also opens up an avenue for precision design of vacancies to prepare novel photocatalytic materials driven under solar light.

Rotation Restricted Emission and Antenna Effect in Single Metal-Organic Frameworks.

Aggregation induced-emission (AIE) and antenna effects are important luminescence behaviors. Thus, investigating their emission mechanisms and revealing their behaviors have become critical but challenging. Here we design and prepare metal-organic frameworks (MOFs) with an AIE ligand (i.e., tetrakis(4-carboxyphenyl)pyrazine (L1)) and Ln3+ ions (including Eu3+, Tb3+, and Gd3+). The emission from L1 is gradually enhanced during the formation of the MOFs because coordination restricts the intramolecular rotation. Thus, the emission is called as coordination-induced emission (CIE) with the same restriction of intramolecular rotation mechanism as AIE. Meanwhile, benzene rings twist to adapt to the MOFs' rigid structure, so the emission blueshifts gradually, as an additional evidence of CIE. Both AIE and CIE are "rotation-restricted emission (RRE)". Eu3+ ions exhibit the strongest emission with gradually enhanced intensity during the formation of L1-Eu MOF. Combined with emission properties from Tb3+ and Gd3+ ions, the antenna effect is verified. We also validate the conditions for the efficient sensitization of Ln3+ ions experimentally and refresh the threshold value of the energy gap between triplet state of a ligand and excited state of Ln3+ ions to 3000 cm-1. Thus, RRE and antenna effects are revealed and validated simultaneously. Because CIE of L1 and antenna effect emission from Eu3+ ions are enhanced simultaneously as strong dual emissions, ratiometric fluorescence detection is realized with the detection of arginine as a model. Our results incorporate AIE and CIE into RRE, which provides explicit information for the construction and application of emission systems with AIE ligands as building blocks. MOFs are also extended to explore the emission mechanism and the energy transfer between ligands and metal ions.

Carbon Dots, Unconventional Preparation Strategies, and Applications Beyond Photoluminescence.

Carbon dots (C-dots) are generally separated into graphene quantum dots (GQDs) and carbon nanodots (CNDs) based on their respective top-down and bottom-up preparation processes. However, GQDs can be prepared by carbonization of small-molecule precursors as revealed with unconventional preparation strategies. Thus, it is their structures rather than their precursors and preparation strategy that govern whether C-dots are GQDs or CNDs. Here, the composites, structure, and electronic properties of C-dots are discussed. C-dots generally consist of a graphite-like core and amorphous oxygen-containing shell. When graphite becomes C-dots, its conduction and valence bands are separated, and the quantum confinement effect appears. Combined with the light-harvesting ability inherited from graphite, electrons in the core of C-dots are transferred from conduction to valence bands, leading to electron-hole pair formation upon light excitation. The photoexcitation activities, such as photovoltaic conversion, photocatalysis, and photodynamic therapy, are influenced by the electronic properties of the core. Different to the semiconductor properties of core, the C-dot shell is electrochemically active, leading to electrochemiluminescence (ECL). The oxygen-containing groups in shell can conjugate to functional species for use in imaging and therapy. The applications of C-dots beyond photoluminescence, including ECL, solar photovoltaics, photocatalysis, and theranostics, are reviewed.

Lab-on-MOFs: Color-Coded Multitarget Fluorescence Detection with White-Light Emitting Metal-Organic Frameworks under Single Wavelength Excitation.

Multitarget assay with single detection modality from individual stimulation mode has aroused great attention. Here, we realize multitarget detection with the color change as signal source from single white light-emitting metal-organic frameworks (MOFs) under single wavelength excitation for the first time. The white light-emitting MOFs are prepared by carefully tuning the ratio of Eu3+, Tb3+, and Dy3+ ions to obtain trimetal MOFs; 5-boronoisophthalic acid (5-bop) provides additional selectivity as ligand. Based on antenna effect, 5-bop is excited to produce its triplet-state, which sensitizes the Ln3+ ions for the white emission. Thus, all of the fluorescence emission is achieved under single wavelength excitation at 275 nm, while any factors affecting the procedure result in the modulation of emission for diverse wavelengths. The trimetal MOFs display distinctive emission colors after interacting with different targets, including metal ions, anions, small molecule, and even biomolecule as a Lab-on-MOFs system. This system shows higher integration degree and simpler preparation and sensing procedures than other multitarget detection strategies.

Ratiometric Fluorescence Sensing and Real-Time Detection of Water in Organic Solvents with One-Pot Synthesis of Ru@MIL-101(Al)-NH2.

Ratiometric fluorescence detection attracts much attention because of its decreased environmental influence and easy-to-differentiate color and intensity change. Herein, a guest-encapsulation metal-organic framework (MOF), Ru@MIL-NH2, is prepared with 2-aminoterephthalic acid, AlCl3, and Ru(bpy)32+ by a simple one-pot method for ratiometric fluorescence sensing of water in organic solvents. The rational selection of the excitation wavelength provides dual emission at 465 and 615 nm from Ru@MIL-NH2 under a single excitation of 300 nm. High sensitivity, low detection limit (0.02% v/v), wide response range (0-100%), and fast response (less than 1 min) are obtained for ratiometric fluorescence sensing of water under single excitation with Ru@MIL-NH2 as the probe. Moreover, the result of water content is independent of the concentration of Ru@MIL-NH2 as the merit of ratiometric fluorescence detection. The response mechanism reveals that the protonation of the nitrogen atom of the MIL-NH2, the π-conjugation system, and the stable fluorescence of Ru(bpy)32+ achieve the ratiometric fluorescence. The analysis of real spirit samples confirms the proposed method. A test strip is prepared with Ru@MIL-NH2 for convenient use. We believe that such turn-on ratiometric host-guest MOFs and the rational selection of excitation wavelength will offer guidance for ratiometric fluorescence detection with wide applications.

Boric-Acid-Functional Lanthanide Metal-Organic Frameworks for Selective Ratiometric Fluorescence Detection of Fluoride Ions.

Here, we report that boric acid is used to tune the optical properties of lanthanide metal-organic frameworks (LMOFs) for dual-fluorescence emission and improves the selectivity of LMOFs for the determination of F- ions. The LMOFs are prepared with 5-boronoisophthalic acid (5-bop) and Eu3+ ions as the precursors. Emission mechanism study indicates that 5-bop is excited with UV photons to produce its triplet state, which then excites Eu3+ ions for their red emission. This is the general story of the antenna effect, but electron-deficient boric acid decreases the energy transfer efficiency from the triplet state of 5-bop to Eu3+ ions, so dual emission from both 5-bop and Eu3+ ions is efficiently excited at the single excitation of 275 nm. Moreover, boric acid is used to identify fluoride specifically as a free accessible site. The ratiometric fluorescent detection of F- ions is validated with the dual emission at single excitation. The LMOFs are very monodisperse, so the determination of aqueous F- ions is easily achieved with high selectivity and a low detection limit (2 µM). For the first time, we reveal that rational selection of functional ligands can improve the sensing efficiency of LMOFs through tuning their optical property and enhancing the selectivity toward targets.

Fluorescent Imaging-Guided Chemotherapy-and-Photodynamic Dual Therapy with Nanoscale Porphyrin Metal-Organic Framework.

Imaging-guided therapy systems (IGTSs) are revolutionary techniques used in cancer treatment due to their safety and efficiency. IGTSs should have tunable compositions for bioimaging, a suitable size and shape for biotransfer, sufficient channels and/or pores for drug loading, and intrinsic biocompatibility. Here, a biocompatible nanoscale zirconium-porphyrin metal-organic framework (NPMOF)-based IGTS that is prepared using a microemulsion strategy and carefully tuned reaction conditions is reported. A high content of porphyrin (59.8%) allows the achievement of efficient fluorescent imaging and photodynamic therapy (PDT). The 1D channel of the Kagome topology of NPMOFs provides a 109% doxorubicin loading and pH-response smart release for chemotherapy. The fluorescence guiding of the chemotherapy-and-PDT dual system is confirmed by the concentration of NPMOFs at cancer sites after irradiation with a laser and doxorubicin release, while low toxicity is observed in normal tissues. NPMOFs are established as a promising platform for the early diagnosis of cancer and initial therapy.

Carbon quantum dot stabilized gadolinium nanoprobe prepared via a one-pot hydrothermal approach for magnetic resonance and fluorescence dual-modality bioimaging.

Magnetic resonance imaging (MRI) is used extensively for clinical diagnoses. It is critical to design and develop highly efficient MR contrast agents with simple preparation procedure, low toxicity, and high biocompatibility. Here, we report a carbon quantum dots (CQDs)-stabilized gadolinium hybrid nanoprobe (Gd-CQDs) prepared via a one-pot hydrothermal treatment of the mixture of citrate acid, ethanediamine, and GdCl3 at 200 °C for 4 h. In vitro and in vivo tests confirmed their low toxicity and high biocompatibility. Gd-CQDs were observed to have a higher MR response than gadopentetic acid dimeglumine (Gd-DTPA) because of their high Gd content and hydrophilicity. Moreover, the fluorescence of CQDs was remained in Gd-CQDs. The in vivo MR and fluorescence dual-modality imaging of Gd-CQDs was confirmed with zebrafish embryo and mice as models. The modification of Gd-CQDs with arginine-glycine-aspartic acid (RGD) tripeptide provided a high affinity to U87 cancer cells for targeted imaging. Whereas the MR response showed a depth penetration and spatial visualization, fluorescence revealed the fine distribution of Gd-CQDs in tissues because of its high resolution and sensitivity. We found that Gd-CQDs distributed in the tissues in a heterogeneous mode: they entered into the tissue cells but were observed less in the extracellular matrix. The MR and fluorescence dual-modality imaging of Gd-CQDs makes them a potential contrast agent for clinic applications because of their simple preparation procedure, ease of functionalization, high contrast efficiency, low toxicity, and high biocompatibility.