An Anionic Porous Indium-Organic Framework with Nitrogen-Rich Linker for Efficient and Selective Removal of Trace Cationic Dyes.

Metal-organic frameworks (MOFs) with porosity and functional adjustability have great potential for the removal of organic dyes in the wastewater. Herein, an anionic porous metal-organic framework (MOFs) [Me2NH2]2In2[(TATAB)4(DMF)4]·(DMF)4(H2O)4 (HDU-1) was synthesized, which is constructed from a [In(OOC)4]- cluster and a nitrogen-rich linker H3TATAB (4,4',4″-s-triazine-1,3,5-triyltri-p-aminobenzoic acid). The negatively charged [In(OOC)4]- cluster and uncoordinated -COOH on the linker result in one unit cell of HDU-1 having 8 negative sites. The zeta potential of -20.8 mV dispersed in pure water also shows that HDU-1 possesses negatively charged surface potential. The high electronegativity, water stability, and porosity of HDU-1 can facilitate the ion-exchange and Coulombic interaction. As expected, the HDU-1 exhibits high selectivity and removal rates towards trace cationic dyes with suitable size, such as methylene blue (MB) (96%), Brilliant green (BG) (99.3%), and Victoria blue B (VB) (93.6%).

Highly Sensitive Adsorption and Detection of Iodide in Aqueous Solution by a Post-Synthesized Zirconium-Organic Framework.

Effective methods of detection and removal of iodide ions (I-) from radioactive wastewater are urgently needed and developing them remains a great challenge. In this work, an Ag+ decorated stable nano-MOF UiO-66-(COOH)2 was developed for the I- to simultaneously capture and sense in aqueous solution. Due to the uncoordinated carboxylate groups on the UiO-66-(COOH)2 framework, Ag+ was successfully incorporated into the MOF and enhanced the intrinsic fluorescence of MOF. After adding iodide ions, Ag+ would be produced, following the formation of AgI. As a result, Ag+@UiO-66-(COOH)2 can be utilized for the removal of I- in aqueous solution, even in the presence of other common ionic ions (NO2-, NO3-, F-, SO42-). The removal capacity as high as 235.5 mg/g was calculated by Langmuir model; moreover, the fluorescence of Ag+@UiO-66-(COOH)2 gradually decreases with the deposition of AgI, which can be quantitatively depicted by a linear equation. The limit of detection toward I- is calculated to be 0.58 ppm.

Series of Luminescent Lanthanide MOFs with Regular SHG Performance.

Second-harmonic generation (SHG) is a kind of nonlinear optical phenomenon which has been widely used in optical devices, and factors influencing its signal are very complex. Here, taking advantage of excellent structural designability and overcoming the limitations of various coordinations of lanthanide metals, for the first time a series of lanthanide metal-organic frameworks (Ln-MOFs) with one particular ligand were synthesized and structurally characterized to study the interference of the SHG signal. The optical performance including single-photon fluorescence and SHG was collected and analyzed. It is found that all 13 kinds of Ln-MOFs can be divided into 2 crystal configurations by their individual space groups and Ln-MOFs with coordinated metal atoms from La to Tb possessing the noncentrosymmetric C2 space group exhibit the SHG property, the intensity of which depends on the type of metal atoms, the pumping wavelength, and the size of the single-crystal particles. This is the first time that the relationship between the nonlinear optical properties and the structure, metal atoms, pumping wavelength, crystal size of the whole series of Ln-MOFs is studied systematically, providing a lot of interesting results and enriching the research scope of nonlinear optics and materials science.

Highly Stable Lanthanide Metal-Organic Framework as an Internal Calibrated Luminescent Sensor for Glutamic Acid, a Neuropathy Biomarker.

Glutamic acid (Glu) is the most abundant excitatory neurotransmitter in the central nervous system, and an elevated level of Glu may indicate some neuropathological diseases. Herein, three isomorphic microporous lanthanide metal-organic frameworks (MOFs) [(CH3)2NH2]2[Ln6(µ3-OH)8(BDC-OH)6(H2O)6]·(solv)x (ZJU-168; ZJU = Zhejiang University, H2BDC-OH = 2-hydroxyterephthalic acid, Ln = Eu, Tb, Gd) were designed for the detection of Glu. ZJU-168(Eu) and ZJU-168(Tb) suspensions simultaneously produce the characteristic emission bands of both lanthanide ions and ligands. When ZJU-168(Eu) and ZJU-168(Tb) suspensions exposed to Glu, the fluorescence intensity of ligands increases while the emission of lanthanide ions is almost unchanged. By utilizing the emission of ligands as the detected signal and the emission of lanthanide ions as the internal reference, an internal calibrated fluorescence sensor for Glu was obtained. There is a good linear relationship between fluorescence intensity ratio and Glu concentration in a wide range with the detection limit of 3.6 µM for ZJU-168(Tb) and 4.3 µM for ZJU-168(Eu). Major compounds present in blood plasma have no interference for the detection of Glu. Furthermore, a convenient analytical device based on a one-to-two logic gate was constructed for monitoring Glu. These establish ZJU-168(Tb) as a potential turn-on, ratiometric, and colorimetric fluorescent sensor for practical detection of Glu.

A Terbium Metal-Organic Framework for Highly Selective and Sensitive Luminescence Sensing of Hg2+ Ions in Aqueous Solution.

A series of isomorphic lanthanide metal-organic frameworks (MOFs) Ln(TATAB)⋅(DMF)4 (H2 O)(MeOH)0.5 (LnTATAB, Ln=Eu, Tb, Sm, Dy, Gd; H3 TATAB=4,4',4''-s-triazine-1,3,5-triyltri-p-aminobenzoic acid) have been solvothermally synthesized and structurally characterized. Among these MOFs, TbTATAB exhibits good water stability and a high fluorescence quantum yield. Because mercury ions (Hg2+ ) have a high affinity to nitrogen atoms, and the space between multiple nitrogen atoms from triazine and imino groups is suitable for interacting with Hg2+ ions, TbTATAB shows highly selective and sensitive detection of Hg2+ in aqueous solution with a detection limit of 4.4 nm. Furthermore, it was successfully applied to detect Hg2+ ions in natural water samples.

Direct observation of highly effective hydrogen isotope separation at active metal sites by in situ DRIFT spectroscopy.

In situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was developed for the first time to observe the hydrogen isotope separation behavior at active CuI sites within CuI-MFU-4l, and clear evidence of the preferential adsorption of D2 over H2 was directly captured. More importantly, our results show direct spectral proof to clarify the chemical affinity quantum sieving mechanism of hydrogen isotope separation within porous adsorbents.

Three isostructural hexanuclear lanthanide-organic frameworks for sensitive luminescence temperature sensing over a wide range.

Temperature sensing plays essential roles in both fundamental research and high-tech applications. In this work, three isomorphic hexanuclear lanthanide metal-organic frameworks (Ln-MOFs), Ln(BPDC-xN) (Ln = Eu3+/Tb3+, x = 0, 1, 2) were prepared based on the cluster-based synthesis strategy with three structurally similar dicarboxylate ligands 4,4'-biphenyldicarboxylic acid (H2BPDC-0N), 6-(4-carboxyphenyl)nicotinic acid (H2BPDC-1N), and [2,2'-bipyridine]-5,5'-dicarboxylic acid (H2BPDC-2N) as the organic linkers. The as-synthesized Ln-MOFs were fully characterized using single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), elemental analysis (EA), and Fourier transform infrared spectra (FT-IR). Using a Eu3+/Tb3+ co-doping approach, Eu0.001Tb0.999(BPDC-xN) (x = 0, 1, 2) were identified as potential ratiometric luminescence thermometers. Since there are two suitable distances between the energy donors and acceptors within the framework for efficient energy transfer, all Eu0.001Tb0.999(BPDC-xN) (x = 0, 1, 2) maintain high relative sensitivity over a wide temperature range from 50 K to 300 K.

The ratiometric detection of the biomarker Ap5A for dry eye disease and physiological temperature using a rare trinuclear lanthanide metal-organic framework.

Urgent demand for the prevention and diagnosis of physiological diseases is driving the development of biomarkers and physiological temperature fluorometric sensors. In this paper, a rare trinuclear lanthanide metal-organic framework (MOF), [(CH3)2NH2][Eu3(µ3-OH)(2,6-NDC)3(HCOO)3]·(solv)x (Eu(2,6-NDC), where 2,6-H2NDC = 2,6-naphthalenedicarboxylic acid) was synthesized using reticular chemistry via reducing the symmetry of the organic ligand from axisymmetric 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) to non-axisymmetric 2,6-H2NDC. Eu(2,6-NDC) shows exceptional chemical and thermal stability in acid-base solutions, PBS solution, and boiling water, and even under an air atmosphere up to 300 °C. As-synthesized Eu(2,6-NDC) exhibits ratiometric detection abilities for P1,P5-di(adenosine-5') pentaphosphate (Ap5A), for use as a biomarker of dry eye disease, with a limit of detection (LOD) of 0.031 µM, as well as excellent anti-interference properties. As far as is known, it is the first Ap5A sensor based on MOFs. In addition, the results show that the ratiometric parameters of co-doped Eu0.001Gd0.999(2,6-NDC) deliver a good linear luminescence response to physiological temperatures (20-60 °C) with high sensitivity.

Tailoring the triplet level of isomorphic Eu/Tb mixed MOFs for sensitive temperature sensing.

Three different thermo-responsive fluorescent thermometers were constructed by regulating the triplet energy level of organic ligands in isostructural Eu/Tb mixed MOFs. Among them, a quite unusual and rarely reported temperature-dependent fluorescence behavior was observed in LnBDC-NH2, and Eu0.01Tb0.99NDC is effective in the physiological range with the maximum relative sensitivity of 7.32% °C-1.

Lanthanide metal-organic frameworks with nitrogen functional sites for the highly selective and sensitive detection of NADPH.

A series of isostructural Ln-MOFs, namely Eu(BPDC-xN)(x = 0, 1, 2), with different numbers of nitrogen atoms were designed and synthesized. Due to the strong affinity between the bare phosphate group of NADPH and nitrogen functional sites, the highly selective and sensitive detection of NADPH was realized. Furthermore, as the number of sites was increased, the sensitivity significantly increased, with a detection limit as low as 0.43 µM.

A luminescent ratiometric pH sensor based on a nanoscale and biocompatible Eu/Tb-mixed MOF.

The precise and real-time monitoring of localized pH changes is of great importance in many engineering and environmental fields, especially for monitoring small pH changes in biological environments and living cells. Metal-organic frameworks (MOFs) with their nanoscale processability show very promising applications in bioimaging and biomonitoring, but the fabrication of nanoscale MOFs is still a challenge. In this study, we synthesized a nanoscale mixed-lanthanide metal-organic framework by a microemulsion method. The morphology and size of the NMOF can be simply adjusted by the addition of different amounts of the CTAB surfactant. This NMOF exhibits significant pH-dependent luminescence emission, which can act as a self-referenced pH sensor based on two emissions of Tb3+ at 545 nm and Eu3+ at 618 nm in the pH range from 3.00 to 7.00. The MTT assay and optical microscopy assay demonstrate the low cytotoxicity and good biocompatibility of the nanosensor.

A Two-Photon Luminescent Dye-Loaded Metal-Organic Framework for Physiological Temperature Sensing within Biological Windows.

Luminescent temperature sensing in biological windows is uniquely superior compared to traditional temperature sensing methods because the scattering and absorption by skin, tissue and blood is minimal. In this study, the two-photon luminescence from dyes loaded into a metal-organic framework was utilised to achieve physiological temperature sensing within two biological windows. A composite was prepared that can be excited at 1064 nm to emit at 650 nm, well within the two biological windows. The two-photon luminescence intensity at 650 nm has a linear relationship with temperature over the range 20 to 60 °C. In addition, the stability and quantum efficiency were significantly improved after loading into the MOF and, with high temperature resolution, excellent repeatability and low biological toxicity, measurements with this composite has great potential to be applied to physiological temperature sensing in cells or tissues.

A dye encapsulated terbium-based metal-organic framework for ratiometric temperature sensing.

A terbium-based metal-organic framework (MOF) TbTATAB (H3TATAB = 4,4',4''-s-triazine-1,3,5-triyltri-p-aminobenzoic acid) with a 1D channel has been synthesized and structurally characterized. Then, the luminescent dye 7-diethylamino-4-methylcoumarin (C460) was encapsulated into the channel of TbTATAB by an exchange strategy to yield the dual-emitting MOF⊃dye composite TbTATAB⊃C460. Luminescence explorations demonstrated that the composite can be applied as a ratiometric thermometer over a wide temperature range from 100 to 300 K. The unique energy transfer between C460 molecules and Tb3+ enables the TbTATAB⊃C460 thermometer to be highly temperature-sensitive with a maximum relative sensitivity of 4.484% K-1 at 300 K. The composite luminescent thermometer is self-calibrated, colorimetric, reusable and much more thermosensitive than most of the other explored sensors.

Turn-on and Ratiometric Luminescent Sensing of Hydrogen Sulfide Based on Metal-Organic Frameworks.

The sensing of hydrogen sulfide (H2S) has become a long-time challenging task. In this work, we developed a general strategy for sensing of H2S utilizing postsynthetic modification of a nano metal-organic frameworks (MOF) UiO-66-(COOH)2 with Eu3+ and Cu2+ ions. The nano MOF Eu3+/Cu2+@UiO-66-(COOH)2 displays the characteristic Eu3+ sharp emissions and the broad ligand-centered (LC) emission simultaneously. Because H2S can strongly increase the fluorescence of Eu3+ and quench the broad LC emission through its superior affinity for Cu2+ ions, the MOF Eu3+/Cu2+@UiO-66-(COOH)2 exhibits highly sensitive turn-on sensing of H2S over other environmentally and biologically relevant species under physiological conditions. Furthermore, this approach for fluorescent turn-on sensing of H2S is expected to extend to other water-stable MOFs containing uncoordinated -COOH.

Pressure controlled drug release in a Zr-cluster-based MOF.

A robust zirconium-cluster-based metal-organic framework (MOF) ZJU-800 with an excellent drug loading capacity (about 58.80 wt%) has been synthesized. The system shows an adjustable release time of the drug diclofenac sodium from 2 days to 8 days by controlling the degree of compaction between MOF and drug using pressure.