Novel fluorescent supramolecular polymer metallogel based on Al3+ coordinated cross-linking of quinoline functionalized- pillar[5]arene act as multi-stimuli-responsive materials

A novel supramolecular polymer metallogel ( QP5-AlG ) has been constructed by cross-linking of bis-8-hydroxyquinoline functionalized pillar[5]arene with Al³⁺. The metallogel QP5-AlG shows light blue aggregation induced emission (AIE) in DMSO/H₂O binary solution. Interestingly, the QP5-AlG shown multiple external stimuli-responsive behaviors such as temperature, guest compounds, acid, base and so on. The QP5-AlG can be used as a fluorescent material for detection of Fe³⁺, F^-, trifluoroacetic acid (TFA) and triethylamine (TEA) by different fluorescence states (“on” or “off”). The (limits of lowest detection) LOQs of the QP5-AlG for Fe³⁺, F^-, TFA and TEA are in the range of 4.39 × 10^-9-1.82 × 10^-7 M. More interestingly, a QP5-AlG -based rewritable and erasable fluorescent platform was demonstrated, which offers a potential testbed for performing “write-erase-write” cycles multiple times. This study provides insight into the development of novel multifunctional supramolecular materials.     

Tunable Aggregation-Induced Emission of Imidazole Hydrazones by pH and Anions

Aggregation-induced emission (AIE) materials have drawn great attention for applications as organic light-emitting diodes (OLED) and probes. The applications are, however, restricted by the complex syntheses and hydrophobic properties. Herein, a one-step synthesis of an AIE material based on imidazole hydrazone is assessed. Protonation of the imidazole-H leads to emission color change from yellow to green in the solid state. The emission color is recovered upon imidazole-H⁺ deprotonation. Moreover, the emission wavelength shifts from 532 to 572 nm by anion exchange. In addition, an enhanced emission (Φ_F up to 22.6 %) was obtained with the Br⁻ anion compared with NTf₂⁻, SbCl₅⁻, PF₆⁻, and OTf⁻ anions. X-ray crystallography studies together with theoretical calculations show that the enhanced emission of hydrazone salts arises from strong hydrogen bonding between the hydrazone proton and the halide ion (Cl⁻ or Br⁻).     

Selective detection of mercury(II) and methylmercury(II) via coordination-induced emission of a small-molecule probe

Mercury is one of the major toxic pollutants and has many adverse effects on human health. The main mercury species in the environment or in living organisms are inorganic mercuric ion (Hg²⁺) and organic methylmercury (CH3Hg+). Detection of the two mercury ions is a particularly active topic in the molecular sensing field during the past decade. However, efficient sensors that can sensitively detect and discriminate the two species are rare. In this work, we adopt the concept of restriction of intramolecular rotations which is the basis of aggregation induced emission, and design a molecular probe with pyridyl group as the chelating unit and 1,8-naphthalimide as the fluorescent unit for the detection of both Hg²⁺ and CH₃Hg⁺. When the probe is free in solution, it exhibits weak fluorescence because free intramolecular rotations of the 1,8-naphthalimide moieties non-radiatively annihilate its excited state. However, upon coordination with Hg²⁺ or CH₃Hg⁺, the rotation of 1,8-naphthalimide moieties would be restricted due to the chelation between 1,8-naphthalimide and Hg²⁺ or CH₃Hg⁺, leading to significantly enhanced fluorescent emission. The response induced by Hg²⁺ is much stronger than CH₃Hg⁺; but for specific detection of CH₃Hg⁺, we introduced a T-rich DNA fragment which could completely mask Hg²⁺ in solution. Furthermore, we have employed the sensor for confocal imaging of Hg²⁺ and CH₃Hg⁺in immobilized cells. We expect the probe design tactics can be generally useful for sensing many other analytes.     

Cooperative coupling of photocatalytic production of H2O2 and oxidation of organic pollutants over gadolinium ion doped WO3 nanocomposite

This work reported the lanthanide ion (Gd³⁺) doped tungsten trioxide (Gd-WO₃) nanocrystal for remarkable promoted photocatalytic degradation of organic pollutants and simultaneous in-situ H₂O₂ production. With doped lanthanide ion (Gd³⁺), Gd-WO₃ showed a much broad and enhanced solar light absorption, which not only promoted the photocatalytic degradation efficiency of organic compounds, but also provided a suitable bandgap for direct reduction of oxygen to H₂O₂. Additionally, the isolated Gd³⁺ on WO₃ surface can efficiently weaken the *OOH binding energy, increasing the activity and selectivity of direct reduction of oxygen to H₂O₂, with a rate of 0.58 mmol L⁻¹ g⁻¹ h⁻¹. The in-situ generated H₂O₂ can be subsequently converted to ^•OH based on Fenton reaction, further contributed to the overall removal of organic pollutants. Our results demonstrate a cascade photocatalytic oxidation-Fenton reaction which can efficiently utilize photo-generated electrons and holes for organic pollutants treatment.     

Highly dispersed Mn2O3−Co3O4 nanostructures on carbon matrix as heterogeneous Fenton-like catalyst

This work reports the synthesis of various carbon (Vulcan XC-72 R) supported metal oxide nanostructures, such as Mn₂O₃, Co₃O₄ and Mn₂O₃−Co₃O₄ as heterogeneous Fenton-like catalysts for the degradation of organic dye pollutants, namely Rhodamine B (RB) and Congo Red (CR) in wastewater. The activity results showed that the bimetallic Mn₂O₃−Co₃O₄/C catalyst exhibits much higher activity than the monometallic Mn₂O₃/C and Co₃O₄/C catalysts for the degradation of both RB and CR pollutants, due to the synergistic properties induced by the Mn−Co and/or Mn (Co)−support interactions. The degradation efficiency of RB and CR was considerably increased with an increase of reaction temperature from 25 to 45°C. Importantly, the bimetallic Mn₂O₃−Co₃O₄/C catalyst could maintain its catalytic activity up to five successive cycles, revealing its catalytic durability for wastewater purification. The structure–activity correlations demonstrated a probable mechanism for the degradation of organic dye pollutants in wastewater, involving •OH radical as well as Mn²⁺/Mn³⁺ or Co²⁺/Co³⁺ redox couple of the Mn₂O₃−Co₃O₄/C catalyst.     

Rational design of an AIE-active metal-organic framework for highly sensitive and portable sensing nitroaromatic explosives

Herein, we report a new metal-organic framework with an AIE ligand (H₄TCPP = 2,3,5,6-tetra-(4-carboxyphenyl)pyrazine) and Mg²⁺ ions, that is, [Mg₂(H₂O)₄TCPP]·DMF·5CH₃CN (Mg-TCPP, TCPP = tetra-(4-carboxyphenyl)pyrazine) for detection of nitroaromatic explosives. Due to the coordination effect and restricted intramolecular rotation, Mg-TCPP exhibits bright blue light. As a fluorescent sensor, Mg-TCPP exhibits high selectivity and sensitivity for sensing 2,4,6-trinitrophenol (TNP) by quenching behaviors with the Stern-Volmer quenching constant (K_SV) of 3.63×10⁵ L/mol and achieves the low limit of detection of 25.6 ppb, which is beyond most of the previously reported fluorescent materials. Notably, the portable Mg-TCPP films are prepared and it can be used for rapid and sensitive TNP detection in a variety of environments including organic solvent and aqueous solution. Moreover, TNP vapor can be detected within 3 min by naked eye and the film could be regenerated under simple solvent cleaning.     

A ratiometric fluorescent chemosensor for Al in aqueous solution based on aggregation-induced emission and its application in live-cell imaging

A ratiometric fluorescent chemosensor 1 was developed for the detection of Al³⁺ in aqueous solution based on aggregation-induced emmision (AIE). The chemosensor showed the fluorescence of its aggregated state and Al³⁺-chelated soluble state in the absence and in the presence of Al³⁺, respectively, and resulted in a fluorescence ratio (I₄₆₁/I₅₃₇) response to Al³⁺ in neutral aqueous solution at a detection limit as low as 0.29 μmol L⁻¹. The method was also highly selective to Al³⁺ over other physiological relevant metal ions investigated in this study. Taking advantage of its AIE characteristics, the chemosensor was successfully applied on test papers for simple and rapid detection of Al³⁺. Moreover, the application of 1 for the imaging of Al³⁺ in living cells by ratiometric fluorescence changes was also achieved.     

Probing phosphate ion via the europium(III)-modulated fluorescence of gold nanoclusters

Fluorescent gold nanoclusters (Au-NCs) were synthesized by a one-pot method using 11-mercaptoundecanoic acid as a reducing and capping reagent. It is found that the red fluorescence of the Au-NCs is quenched by the introduction of Eu(III) at pH 7.0, but that fluorescence is restored on addition of phosphate. The Au-NCs were investigated by transmission electron microscopy and fluorescence photographs. The effect of pH on fluorescence was studied in the range from pH 6 to 10 and is found to be strong. Based on these findings, we have developed an assay for phosphate. Ions such as citrate, Fe(CN)₆ ³⁻, SO₄ ²⁻, S₂O₈ ²⁻, Cl⁻, HS⁻, Br⁻, AcO⁻, NO₂ ⁻, SCN⁻, ClO₄ ⁻, HCO₃ ⁻, NO₃ ⁻, Cd²⁺, Ba²⁺, Zn²⁺, Mg²⁺, and glutamate do not interfere, but ascorbate and Fe³⁺ can quench Au-NCs fluorescence. The fluorescent nanocluster probe responds to phosphate in the range from 0.18 to 250 μM, and the detection limit is 180 nM. The probe also responds to pyrophosphate and ATP.

Off/on fluorescence sensor for phosphate based on Eu³⁺-modulated Au NCs thanks to the competition of oxygen-donor atoms from phosphate with those from the carboxylate groups was developed

     

Designing 3D-MoS2 Sponge as Excellent Cocatalysts in Advanced Oxidation Processes for Pollutant Control

3D-MoS₂ can adsorb organic molecules and provide multidimensional electron transport pathways, implying a potential application for environment remediation. Here, we study the degradation of aromatic organics in advanced oxidation processes (AOPs) by a 3D-MoS₂ sponge loaded with MoS₂ nanospheres and graphene oxide (GO). Exposed Mo⁴⁺ active sites on 3D-MoS₂ can significantly improve the concentration and stability of Fe²⁺ in AOPs and keep the Fe³⁺/Fe²⁺ in a stable dynamic cycle, thus effectively promoting the activation of H₂O₂/peroxymonosulfate (PMS). The degradation rate of organic pollutants in the 3D-MoS₂ system is about 50 times higher than without cocatalyst. After a 140 L pilot-scale experiment, it still maintains high efficiency and stable AOPs activity. After 16 days of continuous reaction, the 3D-MoS₂ achieves a degradation rate of 120 mg L⁻¹ antibiotic wastewater up to 97.87 %. The operating cost of treating a ton of wastewater is only US$ 0.33, suggesting huge industrial applications.     

Turn-on fluorescence sensor based on the aggregation of pyrazolo[3,4-b]pyridine-based coumarin chromophores induced by Hg

We developed a new fluorescent sensor (PPC-S) for Hg²⁺ based on the aggregation-induced emission (AIE) of pyrazolo[3,4-b]pyridine-based coumarin chromophore (PPC-O). Given the desulfurization reaction with Hg²⁺, AIE inactive PPC-S can be transformed into PPC-O with AIE activity, which can be employed for the fluorescence turn-on detection of Hg²⁺ with satisfactory selectivity and sensitivity in aqueous solutions.     

Simple and selective determination of arsenite and arsenate by electrospray ionization mass spectrometry

Arsenic pollution of public water supplies has been reported in various regions of the world. Recently, some cancer patients are treated with arsenite (As^III); most Japanese people consume seafoods containing large amounts of negligibly toxic arsenic compounds. Some of these arsenic species are metabolized, but some remain intact. For the determination of toxic As^III, a simple, rapid and sensitive method has been developed using electrospray ionization mass spectrometry (ESI-MS). As^III was reacted with a chelating agent, pyrrolidinedithiocarbamate (PDC, C₄H₈NCSS^-) and tripyrrolidinedithiocarbamate-arsine, As(PDC)₃, extracted with methyl isobutyl ketone (MIBK). A 1 μL aliquot of MIBK layer was directly injected into ESI-MS instrument without chromatographic separation, and was detected within 1 min. Arsenate (As^V) was reduced to As^III with thiosulfate, and then the total inorganic As was quantified as As^III. This method was validated for the analysis of urine samples. The limit of detection of As was 0.22 μg L⁻¹ using 10 μL of sample solution, and it is far below the permissible limit of As in drinking water, 10 μg L⁻¹, recommended by the WHO. Results were obtained in < 10 min with a linear calibration range of 1-100 μg L⁻¹. Several organic arsenic compounds in urine did not interfere with As^III detection, and the inorganic As in the reference materials SRM 2670a and 1643e were quantified after the reduction of As^V to As^III.     

A Water‐Stable Terbium(III)–Organic Framework as a Chemosensor for Inorganic Ions,Nitro‐Containing Compounds and Antibiotics in Aqueous Solutions

Effective detection of organic/inorganic pollutants, such as antibiotics, nitro‐compounds, excessive Fe³⁺ and MnO₄^?, is crucial for human health and environmental protection. Here, a new terbium(III)–organic framework, namely [Tb(TATAB)(H₂O)]?2H₂O ( Tb‐MOF , H₃TATAB=4,4′,4′′‐s‐triazine‐1,3,5‐triyltri‐m‐aminobenzoic acid), was assembled and characterized. The Tb‐MOF exhibits a water‐stable 3D bnn framework. Due to the existence of competitive absorption, Tb‐MOF has a high selectivity for detecting Fe³⁺, MnO₄^?, 4‐nirophenol and nitroimidazole (ronidazole, metronidazole, dimetridazole, ornidazole) in aqueous through luminescent quenching. The results suggest that Tb‐MOF is a simple and reliable reagent with multiple sensor responses in practical applications. To the best of our knowledge, this work represents the first Tb^III‐based MOF as an efficient fluorescent sensor for detecting metal ions, inorganic anions, nitro‐compounds, and antibiotics simultaneously.     

Metalo Hydrogen-Bonded Organic Frameworks (MHOFs) as New Class of Crystalline Materials for Protonic Conduction

Recently, proton conduction has been a thread of high potential owing to its wide applications in fuel-cell technology. In the search for a new class of crystalline materials for protonic conductors, three metalo hydrogen-bonded organic frameworks (MHOFs) based on [Ni(Imdz)₆]²⁺ and arene disulfonates (MHOF1 and MHOF2) or dicarboxylate (MHOF3) have been reported (Imdz=imidazole). The presence of an ionic backbone with charge-assisted H-bonds, coupled with amphiprotic imidazoles made these MHOFs protonic conductors, exhibiting conduction values of 0.75×10⁻³, 3.5×10⁻⁴ and 0.97×10⁻³ S cm⁻¹, respectively, at 80 °C and 98 % relative humidity, which are comparable to other crystalline metal-organic framework, coordination polymer, polyoxometalate, covalent organic framework, and hydrogen-bonded organic framework materials. This report initiates the usage of MHOF materials as a new class of solid-state proton conductors.     

A multifunctional aggregation-induced emission (AIE)-active fluorescent chemosensor for detection of Zn2+ and Hg2+

An aggregation-induced emission (AIE)-active fluorescent chemosensor based on a tetraphenylethene (TPE) unit has been successfully designed and synthesized. Interestingly, the luminogen could detect Zn²⁺ selectively in a THF solution with the detection limit of 1.24 × 10⁻⁶ mol L⁻¹. Meanwhile, the luminogen could also detect Hg²⁺ selectively in a THF-water mixture with the water content of 90%, and the detection limit was 2.55 × 10⁻⁹ mol L⁻¹. Furthermore, the solid-state mechanochromic fluorescence behavior of the luminogen was investigated systematically. Indeed, the AIE-active luminogen also exhibited reversible mechanofluorochromic phenomenon involving fluorescent color change from blue to green, and powder X-ray diffraction results indicated that the switchable morphology conversion between crystalline and amorphous states was responsible for this mechanochromism phenomenon.     

Supramolecular Assemblies with Aggregation-Induced Emission Properties for Sensing and Detection

The fabrication of new supramolecular materials for real-time detection of analytes including ions, organic pollutants, gases, biomolecules, and drugs is of pivotal importance in industrial manufacture, clinical treatment, and environmental remediation. Incorporating fluorescent molecules with distinct aggregation-induced emission (AIE) effects into supramolecular assemblies has received much attention over the past two decades, owing to the remarkable performance of the AIE-active supramolecular materials in sensing and detection. In this minireview, we summarize the recent progress of superior detection systems on the basis of supramolecular assemblies accompanied with AIE features. We envision that this minireview will be helpful and timely for relevant researchers to stimulate new thinking for constructing new AIE-based supramolecular materials with advanced architectures for effective sensing and detection.     

Synthesis and characterization of zirconium(IV) 4-amino, 3-hydroxy naphthalene sulfonate ion exchanger: Quantitative separation of mercury from numerous metal ions

Zirconium (IV) 4-amino, 3-hydroxy naphthalene sulfonate ion-exchanger has been synthesized by mixing equimolar solutions of zirconium oxychloride and ammonium hydroxide in molar ratio 1:1.66 to get a gelatinous material. To this were added varying amounts of 4-amino, 3-hydroxynaphthalene sulphonic acid (ANSA) with constant stiring in order to ensure a complete adsorption of organic molecules to the surface of the gel. The ion exchange material shows a dual character possessing both cation and anion exchange capacities. The former is attributed to the dissociation of strong sulphonic groups from ANSA and acidic sites of hydrous oxide gel, the later one is due to the formation of a positive charge on the nitrogen atom ; in addition, the material may have a sorption capacity. A preliminary investigation to characterize the material has been carried out which includes IR, TGA, DTA and X-ray diffraction. On the basis of distribution coefficients the separation of Hg⁺² from Zn²⁺, Al²⁺, Ni²⁺, Ce⁴⁺, Mg²⁺, Pb²⁺, Mn²⁺, Cu²⁺, has been achieved. The decreasing sequence of Kd values for different anionic species are found to be PO₄³⁻ > Fe (CN)₆³⁻ > MnO₄⁻ > VO₃⁻ > AsO₄³⁻ > C₂O₄²⁻ and for halides Cl⁻ > Br⁻ > I⁻.     

A 2D cadmium metal–organic framework: Synthesis,structure and luminescence sensing for chromate,permanganate, cupric,silver and ferric

A multi-responsive Cd metal–organic framework {[Cd (ttpe)(H₂O)(ip)]•4H₂O•DMAC}_n ( 1•4H ₂ O•DMAC ) was synthesized using hydrothermal method (ttpe = 1,1,2,2-tetra(4-(1H-1,2,4-triazol-1-yl)phenyl)ethylene, ip = isophthalate, DMAC = N,N-dimethylacetamide), and characterized. 1 exhibits a 2D (4,4) network. The luminescent sensing experimrnts showed that 1•4H ₂ O•DMAC as a new MOF luminescent sensor can detect Cr₂O₇²⁻, CrO₄²⁻, MnO₄⁻, Cu²⁺, Ag⁺ and Fe³⁺ in aqueous solution with simultaneously high efficiency and high sensitivity. The quenching constants K_sv for Cr₂O₇²⁻, CrO₄²⁻, MnO₄⁻, Cu²⁺, Ag⁺ and Fe³⁺ are 4.231 × 10⁴ M⁻¹, 2.471 × 10⁴ M⁻¹, 6.459 × 10³ M⁻¹, 7.617 × 10³ M⁻¹, 1.563 × 10⁴ M⁻¹ and 3.574 × 10⁴ M⁻¹, respectively. The detection limits are 0.094 μM for Cr₂O₇²⁻, 0.108 μM for CrO₄^{2 −} , 0.346 μM for MnO₄⁻, 0.302 μM for Cu²⁺, 0.221 μM for Ag ⁺ , and 0.100 μM for Fe³⁺. 1•4H ₂ O•DMAC exhibits high photocatalytic efficiency for degradation of methylene blue under visible light irradiation.     

Non‐Doped Sky‐Blue OLEDs Based on Simple Structured AIE Emitters with High Efficiencies at Low Driven Voltages

Blue organic light‐emitting diodes (OLEDs) are necessary for flat‐panel display technologies and lighting applications. To make more energy‐saving, low‐cost and long‐lasting OLEDs, efficient materials as well as simple structured devices are in high demand. However, a very limited number of blue OLEDs achieving high stability and color purity have been reported. Herein, three new sky‐blue emitters, 1,4,5‐triphenyl‐2‐(4‐(1,2,2‐triphenylvinyl)phenyl)‐1H‐imidazole (TPEI), 1‐(4‐methoxyphenyl)‐4,5‐diphenyl‐2‐(4‐(1,2,2‐triphenylvinyl)phenyl)‐1H‐imidazole (TPEMeOPhI) and 1‐phenyl‐2,4,5‐tris(4‐(1,2,2‐triphenylvinyl)phenyl)‐1H‐imidazole (3TPEI), with a combination of imidazole and tetraphenylethene groups, have been developed. High photoluminescence quantum yields are obtained for these materials. All derivatives have demonstrated aggregation‐induced emission (AIE) behavior, excellent thermal stability with high decomposition and glass transition temperatures. Non‐doped sky‐blue OLEDs with simple structure have been fabricated employing these materials as emitters and realized high efficiencies of 2.41 % (4.92 cd A⁻¹, 2.70 lm W⁻¹), 2.16 (4.33 cd A⁻¹, 2.59 lm W⁻¹) and 3.13 % (6.97 cd A⁻¹, 4.74 lm W⁻¹) for TPEI, TPEMeOPhI and 3TPEI, with small efficiency roll‐off. These are among excellent results for molecules constructed from the combination of imidazole and TPE reported so far. The high performance of a 3TPEI‐based device shows the promising potential of the combination of imidazole and AIEgen for synthesizing efficient electroluminescent materials for OLED devices.     

A Three-Dimensional Porous Organic Semiconductor Based on Fully sp2-Hybridized Graphitic Polymer

Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three-dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three-dimensional organic polymers is challenging. Now, the synthesis of a three-dimensional π-conjugated porous organic polymer (3D p-POP) using catalyst-free Diels–Alder cycloaddition polymerization followed by acid-promoted aromatization is presented. With a surface area of 801 m² g⁻¹, full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10⁻⁴ S cm⁻¹ upon treatment with I₂ vapor, the 3D p-POP is the first member of a new class of permanently porous 3D organic semiconductors.     

Structural Modulation on NiCo2S4Nanoarray by N Doping to Enhance 2e-ORR Selectivity for Photothermal AOPs and Zn−O2Batteries**

As a H₂O₂ generator, a 2e⁻ oxygen reduction reaction active electrocatalyst plays an important role in the advanced oxidation process to degrade organic pollutants in sewage. To enhance the tendency of NiCo₂S₄ towards the 2e⁻ reduction reaction, N atoms are doped in its structure and replace S²⁻. The result implies that this weakens the interaction between NiCo₂S₄ and OOH*, suppresses O−O bond breaking and enhances H₂O₂ selectivity. This electrocatalyst also shows photothermal effect. Under photothermal heating, H₂O₂ produced by the oxidation reduction reaction can decompose and releaseOH, which degrades organic pollutants through the advanced oxidation process. Photothermal effect induced by the advance oxidation process shows obvious advantages over the traditional Fenton reaction, such as wide pH adaptation scope and low secondary pollutant due to its Fe²⁺ free character. With Zn as anode and the electrocatalyst as cathode material, a Zn−O₂ battery is assembled. It achieves electricity generation and photothermal effect induced by the advance oxidation process simultaneously.