A dual-function [Ru(bpy)3]2+ encapsulated metal organic framework for ratiometric Al3+ detection and anticounterfeiting application.

In this work, a novel composite material (HPU-24@Ru) has been prepared by combining a blue-emission Cd-based metal-organic framework (MOF, [Cd2(TCPE)(DMF)(H2O)3]n, HPU-24) with a red-emission tris (2,2'-bipyridine) dichlororuthenium(II) hexahydrate ([Ru(bpy)3]2+) molecule for ratiometric fluorescence sensing of Al3+ ions in aqueous medium and high-level dynamic anticounterfeiting application. The luminescence measurement results indicated that the fluorescence intensity of HPU-24 at 446 nm showed a red shift in the presence of Al3+ ions, and the new peak appeared at 480 nm and continued to increase with an increase in Al3+ ion concentration. Meanwhile, the fluorescence intensity of [Ru(bpy)3]2+ almost showed no change. The detection limit was calculated as 11.63 µM, which was better than that for the MOF-based Al3+ ions in some reported examples in aqueous media and achieved through strong electrostatic interactions between HPU-24@Ru and Al3+ ions. Moreover, owing to the particularity of the tetrastyryl structure in HPU-24, HPU-24@Ru showed intriguing temperature-dependent emission behavior. This unique structure provides the composite material HPU-24@Ru with attributes for high-level information encryption that make it difficult for counterfeiters to identify all of the right decryption measures.

Reversible mechanochromic studies on AIE-inspired smart materials and their applications in HCHO sensing.

Smart fluorescent materials that respond to external stimuli have received more and more attention because of their excellent optical properties in the field of anti-counterfeiting, information security and fluorescence sensing. Herein, we reported a new stimulus-responsive material, {[Zn4(TCPE)(HTCPE)(DMA)3(OH)(H2O)2]·2DMA·2H2O}n (HPU-21), which showed a series of fluorescence changes under the influence of temperature, pressure and solvents. Combined with the temperature-dependent fluorescence, 1H NMR and 13C NMR spectra, TEM and powder X-ray diffraction results, the fluorescence transformation was mainly attributed to the changes in the twisted ethyl core and the multiple rotational phenyl rings, as well as the aggregation degree. Based on these findings, we designed an adjustable formaldehyde probe with excellent performance. The detection limit of formaldehyde in aqueous solutions is calculated as 35 ppb, which is much lower than the concentration that is harmful to health (20 ppm). The extremely high sensitivity to formaldehyde makes it have potential application prospects in practical formaldehyde detection.

A Robust PVDF-Assisted Composite Membrane for Tetracycline Degradation in Emulsion and Oil-Water Separation.

Tetracycline (TC) contamination in water has progressively exacerbated the environmental crisis. It is urgent to develop a feasible method to solve this pollution in water. However, polluted water often contains oil. This paper reported a glass fiber (FG)-assisted polyvinylidene fluoride (PVDF) hybrid membrane with dual functions: high TC degradation efficiency in emulsion and oil-water separation. It can meet the catalytic degradation of tetracycline in complex water. This membrane was decorated by coating the glass fiber with PVDF solution containing hydrophilic graphene oxide hybridized NH2-MIL-101(Fe) particles. Moreover, due to its strong mechanical strength enhanced by the glass fiber, it can be reused as TC degradation catalysts for dozens of times without cracking. Thanks to the hydrophobicity of PVDF and the surface pore size of MOFs, the prepared membrane showed a good oil-water separation performance. Besides, the hydrophilic graphene oxide (GO) and NH2-MIL-101(Fe) improved the membrane's anti-fouling performance, allowing it to be reused as the separation membrane. Therefore, the outstanding stability and recoverability of the membrane make it as a fantastic candidate material for large-scale removal of TC as well as oil-water separation application.

Application in Anticounterfeiting for Multistimuli Smart Luminescent Materials Based on MOF-on-MOF.

The generation of smart responsive materials that can perform multiple drastic optical outputs upon different triggers provides a good platform to encode and hide the information and create multilevel security. In this paper, a smart multiresponsive MOF-on-MOF material was reported using one MOF (HPU-14) as a platform to grow ZIF-8 on the outer layer, combining different emitter centers such as anthracene (ANT) and lanthanide ions (Ln3+) confined into two MOFs. Due to the existence of ANT in the pores of ZIF-8, this composite material can exhibit reversible photoswitching behavior under a 365 nm ultraviolet (UV) lamp and enable "resetting and reusing" dynamic anticounterfeiting application. Meanwhile, when treated by an acid/alkali gas, this material can also display reversible switching behavior under 254 nm UV irradiation, which is attributed to the loading of Ln3+ on HPU-14. We demonstrated that this excellent practical anticounterfeiting material can decipher the right information only by following a strict stimuli sequence. Therefore, this MOF-on-MOF material synthesis technology for sophisticated counterfeiters, which makes the protected information highly secure, could open a new way to design multilevel anticounterfeiting materials.

An AIRE-active far-red ratiometric fluorescent chemosensor for specifically sensing Zn2+ and resultant Zn2+ complex for subsequent pyrophosphate detection in almost pure aqueous media.

A simple Schiff-base fluorescent chemosensor (1) was synthesized by the reaction of 3-amino-pyrazine-2-carbohydrazide and 7-diethylamino-3-formylcoumarin; the sensor 1 displayed a notable green emission at 524 nm in DMSO and an aggregation-induced ratiometric emission (AIRE) at 555 nm in an almost buffered aqueous media (0.5% DMSO content). The AIRE of 1 was quenched following binding to Zn2+ ions, while the fluorescence emission in the far-red region was evidently enhanced at 628 nm. Notably, the ratiometric signal output could be utilized to specifically distinguish Zn2+ among various metal ions. Moreover, the 1-Zn2+ complex was effectively employed as a fluorescent ratiometric chemosensor for pyrophosphate (PPi) detection. The detection limit was 3.52 µM and 2.45 µM for Zn2+ and PPi, respectively. The binding mechanism was evaluated by 1H NMR, ESI-MS, single-crystal X-ray diffraction, TEM, time-resolved fluorescence spectrophotometry, and density functional theory studies. Overall, owing to its sensitive fluorescence behavior, cell imaging studies demonstrated that this sensor is capable of sensing Zn2+ and PPi in living cells.

Postsynthesis Strategy of Functional Zn-MOF Sensors for the Detection of ClO- and DPA.

Active species were introduced into MOFs to prepare multifunctional fluorescent probes by a stepwise postsynthetic modulation strategy. First, two-dimensional HPU-16 (HPU = Henan Polytechnic University; HPU-16 = Zn(L)2(H2O); HL = 2-(5-pyridin-4-yl-5H-[1,2,4]triazol-3-yl)-pyrazine) was transformed into three-dimensional HPU-17 ({Zn3(L)2(btc)2(H2O)}n) through a crystal dissolution-recrystallization process. Second, linker replacement was used to introduce -NH2 into the HPU-17 to generate functional NH2-HPU-17 via a single-crystal to single-crystal transformation. The functional amino groups caused NH2-HPU-17 to show a significant response to ClO-. Because of the interaction of amino groups and ClO-, the fluorescence of NH2-HPU-17 gradually changed from blue to yellow-green. More interestingly, NH2-HPU-17 could encapsulate Tb3+ and sensitize the visible-emitting characteristic fluorescence of Tb3+ in aqueous solution. Then, newly generated Tb3+@NH2-HPU-17 could serve as an effective probe for the determination of DPA. This work paves a new way for the design and modulation of ratiometric fluorescence probes for the selective and sensitive detection of special molecules.

Enhanced Acetone Sensing Property of a Sacrificial Template Based on Cubic-Like MOF-5 Doped by Ni Nanoparticles.

Studying an acetone sensor with prominent sensitivity and selectivity is of great significance for the development of portable diabetes monitoring system. In this paper, cubic-like NiO/ZnO composites with different contents of Ni2+ were successfully synthesized by modifying MOF-5 with Ni2+-doped. The structure and morphology of the prepared composites were characterized by XRD, XPS, and SEM. The experimental results show that the NiO/ZnO composite showed an enhanced gas sensing property to acetone compared to pure ZnO, and the composites showed the maximum response value when Ni2+ loading amount was 5 at%. The response value of the 5% NiO/ZnO composite to acetone (500 ppm) at the optimum operating temperature (340 °C) is 7.3 times as that of pure ZnO. At the same time, the 5% NiO/ZnO composite has excellent selectivity and reproducibility for acetone. The gas sensing mechanism of the heterojunction sensor was described.

A luminescent terbium coordination complex as multifunctional sensing platform.

In this paper, we report the synthesis of a multifunctional fluorescent probe Tb-CP, Tb(HL)(EtOH)2(NO3)2 (HPU-10) (H2L = 2,6-bis-(5-pyridin-4-yl-1H-[1,2,4]triazol-3-yl)- pyridine), and demonstrate that this novel chemosensor has the property of ratiometric detection of Zn2+ and Cd2+. The detection limit of HPU-10 sensing Zn2+ and Cd2+ is 0.319 and 0.965 µM, respectively. The sensing mechanism can be explained by (i) the decomposition of HPU-10 and (ii) the recombination of Zn2+ or Cd2+ with ligand forming 2HL--Zn2+ or 2HL--Cd2+, respectively. Moreover, the fluorescent sensor HPU-10 can detect the nitroaromatic compound 2, 4-DNP via a fluorescence quenching mechanism. The detection limits obtained from linear regression curve plots of 2, 4-DNP is calculated to be 1.69 µM. In addition, the possible use of the probe coated paper for tracing the target analytes has also been presented.

Pyrrole-quinazoline derivative as an easily accessible turn-off optical chemosensor for Cu2+ and resultant Cu2+ complex as a turn-on sensor for pyrophosphate in almost neat aqueous solution.

A simple chemosensor, 6-(1H-pyrrol-2-yl)-5,6-dihydro-benzo[4,5]imidazo[1,2-c]quinazoline (1), was synthesized via simple nucleophilic addition reaction coupled with Schiff base condensation. The probe 1 is aggregation-induced emission-active and could be used as an on-off fluorescence sensor toward Cu2+ in H2O/CH3CN (99.5%, v/v) solution. Furthermore, the resultant Cu2+ complex selectively responded to pyrophosphate (PPi) among various anions based on fluorescent on-off signal. In addition, the probe could be used for detecting Cu2+ and PPi in HeLa cells.

A novel 'turn-on' coumarin-based fluorescence probe with aggregation-induced emission (AIE) for sensitive detection of hydrazine and its imaging in living cells.

An aggregation-induced emission (AIE)- and intramolecular charge transfer (ICT)-based probe 1 (7­hydroxy­3­(3­methyl­isoxazol­5­yl)­chromen­2­one) that is highly selective for N2H4 has been synthesized, exhibiting a 'turn-on' response toward N2H4 in CH3CN/H2O solution. The detection limit of the probe was 2.90 ppb, which was evidently lower than the threshold limit value (10 ppb) recommended by the Environmental Protection Agency. Notably, the sensor could be used for the detection of N2H4 in living cells.

Ratiometric fluorescent probe based on pyrrole-modified rhodamine 6G hydrazone for the imaging of Cu2+ in lysosomes.

A novel rhodamine-based Schiff base derivative was obtained via the simple condensation of substituted formyl-1H-pyrrole and rhodamine 6G hydrazone. Fluorescence resonance energy transfer enabled the subsequent use of the derivative as a naked-eye colorimetric and ratiometric fluorescent sensor for Cu2+ in semi-aqueous solution, and the existence of the morpholine group enabled the further application of the sensor in imaging Cu2+ in the lysosomes of HeLa cells.

Novel rhodamine-based colorimetric and fluorescent sensor for the dual-channel detection of Cu2+ and Co2+/trivalent metal ions and its AIRE activities.

A rhodamine hydrazone 1 bearing coumarin moiety was designed and prepared. Compound 1 exhibited high selectivity toward Co2+ and trivalent metal ions with fluorescence enhancement in CH3OH solution. However, 1 selectively responded to Al3+ in nearly pure H2O media and was further applied to monitor Al3+ in live cells. Moreover, 1 could also act as a colorimetric probe toward Cu2+ in either CH3OH or H2O solution. In addition, sensor 1 displayed aggregation-induced ratiometric emission (AIRE) activities in mixed H2O/CH3OH solution.

Facile Fabrication of Highly Active Magnetic Aminoclay Supported Palladium Nanoparticles for the Room Temperature Catalytic Reduction of Nitrophenol and Nitroanilines.

Magnetically recyclable nanocatalysts with excellent performance are urgent need in heterogeneous catalysis, due to their magnetic nature, which allows for convenient and efficient separation with the help of an external magnetic field. In this research, we developed a simple and rapid method to fabricate a magnetic aminoclay (AC) based an AC@Fe3O4@Pd nanocatalyst by depositing palladium nanoparticles (Pd NPs) on the surface of the magnetic aminoclay nanocomposite. The microstructure and the magnetic properties of as-prepared AC@Fe3O4@Pd were tested using transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and vibrating sample magnetometry (VSM) analyses. The resultant AC@Fe3O4@Pd nanocatalyst with the magnetic Fe-based inner shell, catalytically activate the outer noble metal shell, which when combined with ultrafine Pd NPs, synergistically enhanced the catalytic activity and recyclability in organocatalysis. As the aminoclay displayed good water dispersibility, the nanocatalyst indicated satisfactory catalytic performance in the reaction of reducing nitrophenol and nitroanilines to the corresponding aminobenzene derivatives. Meanwhile, the AC@Fe3O4@Pd nanocatalyst exhibited excellent reusability, while still maintaining good activity after several catalytic cycles.

Facile Fabrication of Magnetic Metal-Organic Framework Composites for the Highly Selective Removal of Cationic Dyes.

In this work, we show a novel magnetic composite material Fe3O4@HPU-9 (HPU-9 = {[Cd(L)0.5(H2O)](DMA)(CH3CN)}n) (H4L = 1,1′-di(3,5-dicarbonylbenzyl)-2,2′bimidazoline, DMA = N,N-dimethylacetamide) constructed by in situ growth of HPU-9 on Fe3O4, which has excellent absorption of cationic dyes from aqueous solution. The Fe3O4@HPU-9 particle possesses a well-defined core-shell structure consisting of a Fe3O4 core (diameter: 190 nm) and a HPU-9 shell (thickness: 10 nm). In the composite, the HPU-9 shell contributes to the capsulation of cationic dyes through electrostatic attractions between HPU-9 and cationic dyes, while the Fe3O4 core serves as magnetic particle. The maximum absorption capacity of Fe3O4@HPU-9 for R6G was 362.318 mg·g−1. The absorption kinetics data were well described by a psedo-second-order model (R² > 0.99), and the equilibrium data were also well fitted to Langmuir isotherm model (R² > 0.99). Our data confirmed that the proposed magnetic composite could be recycled and reused several times without centrifugal separation, making it more convenient, economic and efficient than common adsorbents.

A NIR sensor for cyanide detection and its application in cell imaging.

A novel 'D-π-A' sensor 1 has been designed and prepared via the condensation reaction of 3­ethyl­2­methyl­1,3­benzothiazol­3­ium iodide and 5­nitro­o­vanillin. Upon treatment with cyanide, sensor 1 exhibited a significant near-infrared (NIR) fluorescence quenching at 663nm. The MS, IR, 1H NMR and DFT methods confirmed that the response of 1 to cyanide is due to the nucleophilic addition reaction, which results in the inhibition of the Intramolecular Charge Transfer (ICT) process in the sensor. Furthermore, sensor 1 was used for the determination of CN- in HeLa cells.

A novel visual ratiometric fluorescent sensing platform for highly-sensitive visual detection of tetracyclines by a lanthanide- functionalized palygorskite nanomaterial.

A palygorskite (Pal)-based ratiometric fluorescent nanoprobe is designed in order to establish a real time, on-site visual, and highly sensitive detection method for tetracyclines (TCs). The nanoprobe comprises the green emissive dye molecules embedded in the natural Pal, which serve as the internal reference signal. The potential red-emissive seed-europium (Eu3+) ions are covalently bound on the surface of modified Pal, and they can act as the specific recognition element. The emission intensity of Eu3+ ions significantly increases upon TC addition. The nanoprobe fluorescence changes from green to yellow, orange, or red, thereby accomplishing the visual ratiometric fluorescent detection. This nanoprobe exhibits a high sensitivity with a detection limit of 7.1nM and an excellent selectivity in monitoring the levels of TCs in milk samples. In addition, this nanoprobe is useful for quantitative determination of TCs, and it is not affected with intensity fluctuations due to instrumental or environmental factors. The nanoprobe-immobilized test paper realizes real-time TCs analysis by using a smartphone with an easy-to-access color-scanning APP as the detection platform. Moreover, the reported construction of visual ratiometric detection system follows the sustainable development idea, that is, from nature, for nature, and into the nature.

Quinoline containing acetyl hydrazone: An easily accessible switch-on optical chemosensor for Zn2.

A simple chemosensor, namely, N-((quinolin-8-yl)methylene)acetohydrazide (1) was synthesized and used as an off-on fluorescence sensor, which exhibits high selectivity toward Zn2+ in aqueous media. The probe has large Stokes shift of >200nm, and its detection limit for Zn2+ is 89.3nM. The binding process was confirmed through UV-vis absorption analysis, fluorescence measurements, mass spectroscopy study, 1H NMR spectra and density functional theory calculation. The crystal structures of Zn2+, Ni2+, and Cu2+ complexes based on 1 were determined through X-ray crystallographic analysis. The fluorescent probe was then applied to monitor intracellular Zn2+ in HeLa cells.

A highly sensitive and selective off-on fluorescent chemosensor for hydrazine based on coumarin ß-diketone.

A coumarin-based sensor C1, namely 3-acetoacetylcoumarin was designed, synthesized and applied for hydrazine detection. Hydrazinolysis of the chemosensor gives a fluorescent coumarin-pyrazole product C1-N2H4 [3-(3-methyl-1H-pyrazol-5-yl)coumarin], and thus resulting in a prominent fluorescence off-on response toward hydrazine under physiological conditions. The probe is highly selective toward hydrazine over cations, anions and other biologically/environmentally abundant analytes. The detection limit of the probe is 3.2ppb. The sensing mechanism was supported by 1H NMR, IR, MS and DFT calculation. The application of the fluorescent probe in monitoring intracellular hydrazine in glioma cell line U251 was also demonstrated.

A simple hydrazone as a multianalyte (Cu2+, Al3+, Zn2+) sensor at different pH values and the resultant Al3+ complex as a sensor for F.

A new colorimetric and fluorescence molecular chemosensor based on triazole hydrazone can be used as a multi-probe for selective detection of Al3+, Zn2+, and Cu2+ by monitoring changes in the absorption and fluorescence spectral patterns. Results show that Al3+ and Zn2+ ions can induce remarkable fluorescence enhancement at pH 6.0 and pH 10.0, respectively, while the addition of Cu2+ ions leads to a significant UV-visible absorption enhancement in the visible range at pH 6.0. In addition, the resultant Al3+ complex could act as an 'on-off' fluorescence sensor for F-. The fluorescence sensor was also used to monitor intracellular Al3+, Zn2+, and F- in Hela cells.

AuPd Bimetallic Nanocrystals Embedded in Magnetic Halloysite Nanotubes: Facile Synthesis and Catalytic Reduction of Nitroaromatic Compounds.

In this research, a facile and effective approach was developed for the preparation of well-designed AuPd alloyed catalysts supported on magnetic halloysite nanotubes (HNTs@Fe3O4@AuPd). The microstructure and the magnetic properties of HNTs@Fe3O4@AuPd were confirmed by transmission electron microscopy (TEM), high resolution TEM (HRTEM), energy-dispersive X-ray spectroscopy (EDS), and vibrating sample magnetometry (VSM) analyses. The catalysts, fabricated by a cheap, environmentally friendly, and simple surfactant-free formation process, exhibited high activities during the reduction of 4-nitrophenol and various other nitroaromatic compounds. Moreover, the catalytic activities of the HNTs@Fe3O4@AuPd nanocatalysts were tunable via adjusting the atomic ratio of AuPd during the synthesis. As compared with the monometallic nanocatalysts (HNTs@Fe3O4@Au and HNTs@Fe3O4@Pd), the bimetallic alloyed HNTs@Fe3O4@AuPd nanocatalysts exhibited excellent catalytic activities toward the reduction of 4-nitrophenol (4-NP) to 4-aminophenol. Furthermore, the as-obtained HNTs@Fe3O4@AuPd can be recycled several times, while retaining its functionality due to the stability and magnetic separation property.