Yolk–shell microspheres assembled from Preyssler‐type NaP5W30O11014− polyoxometalate and MIL‐101(Cr) metal–organic framework: A new inorganic–organic nanohybrid for fast and selective removal of cationic organic dyes from aqueous media

Novel inorganic–organic yolk–shell microspheres based on Preyssler‐type NaP₅W₃₀O₁₁₀^14? polyoxometalate and MIL‐101(Cr) metal–organic framework (P₅W₃₀/MIL‐101(Cr)) were synthesized by reaction of K_12.5Na_1.5[NaP₅W₃₀O₁₁₀], Cr(NO₃)₃·9H₂O and terephthalic acid under hydrothermal conditions at 200°C for 24 h. The as‐prepared yolk–shell microspheres were fully characterized using various techniques. All analyses confirmed the incorporation of the Preyssler‐type NaP₅W₃₀O₁₁₀^14? polyoxometalate into the three‐dimensional porous MIL‐101(Cr) metal–organic framework. The results revealed that P₅W₃₀/MIL‐101(Cr) demonstrated rapid adsorption of cationic methylene blue (MB) and rhodamine B (RhB) with ultrahigh efficiency and capacity, as well as achieving rapid and highly selective adsorption of MB from MB/MO (MO = methyl orange), MB/RhB and MB/RhB/MO mixtures. The P₅W₃₀/MIL‐101(Cr) adsorbent not only exhibited a high adsorption capacity of 212 mg g^?1, but also could quickly remove 100% of MB from a dye solution of 50 mg l^?1 within 8 min. The effects of some key parameters such as adsorbent dosage, initial dye concentration and initial pH on dye adsorption were investigated in detail. The equilibrium adsorption data were better fitted by the Langmuir isotherm. The adsorption kinetics was well modelled using a pseudo‐second‐order model. Also, the inorganic–organic hybrid yolk–shell microspheres could be easily separated from the reaction system and reused up to four times without any change in structure or adsorption ability. The stability and robustness of the adsorbent were confirmed using various techniques.     

Effective removal of 2,4,6‐trinitrophenol over hexagonal metal–organic framework NH2‐MIL‐88B(Fe)

A nanostructured organic–inorganic framework, hexagonal NH₂‐MIL‐88B, has been prepared through a facile one‐pot reflux reaction and then it was characterized using various techniques. The as‐prepared sample with high specific surface area (414 m² g^?1) showed excellent adsorption for 2,4,6‐trinitrophenol (TNP) in the liquid phase. Detailed studies of the adsorption kinetics, adsorption mechanism, adsorption isotherm, activation energy and various thermodynamic parameters were conducted. The adsorption mechanism of NH₂‐MIL‐88B for TNP may be ascribed to hydrogen bond interaction, and the complexation between ─OH in TNP and unsaturated Fe(III) on the surface of NH₂‐MIL‐88B. The maximum adsorption capacity of NH₂‐MIL‐88B for TNP based on the Langmuir isotherm was 163.66 mg g^?1. The as‐prepared NH₂‐MIL‐88B adsorbent seems to be a promising material in practice for TNP removal from aqueous solution.     

One‐step synthesized magnetic MIL‐101(Cr) for effective extraction of triazine herbicides from rice prior to determination by liquid chromatography‐tandem mass spectrometry

The magnetic metal‐organic framework MIL‐101(Cr) material‐based solid‐phase extraction method coupled with high‐performance liquid chromatography and tandem mass spectrometry was applied to extract seven triazine herbicides in rices. Fe₃O₄/MIL‐101(Cr) was synthesized using reduction‐precipitation method, in which steps including pre‐synthesis and modification of Fe₃O₄ nanoparticles were by‐passed. Various parameters including extraction solvent type and volume, ultrasonic extraction time, amount of Fe₃O₄/MIL‐101(Cr) microspheres, adsorption time, desorption volume and time were investigated. Under optimal conditions, the proposed method had the limit of detection (S/N = 3) and the limit of quantification (S/N = 10) of 1.08–18.10 and 3.60–60.20 pg/g, respectively. Relative standard deviations calculated for all herbicides with concentrations of 2 and 20 ng/g were in the range of 0.5 to 13% (n = 3). In addition, at the two above‐mentioned concentrations, the method achieved relative recoveries percentages of 79.3 to 116.7% when applied to determine the triazine herbicides in real samples spiked. This rapid, green, non‐polluting, pre‐concentrated extraction method was successfully developed and applied to analyze herbicides in rice samples.     

Mechanochemical Immobilisation of Metathesis Catalysts in a Metal–Organic Framework

A simple, one‐step mechanochemical procedure for immobilisation of homogeneous metathesis catalysts in metal–organic frameworks was developed. Grinding MIL‐101‐NH₂(Al) with a Hoveyda–Grubbs second‐generation catalyst resulted in a heterogeneous catalyst that is active for metathesis and one of the most stable immobilised metathesis catalysts. During the mechanochemical immobilisation the MIL‐101‐NH₂(Al) structure was partially converted to MIL‐53‐NH₂(Al). The Hoveyda–Grubbs catalyst entrapped in MIL‐101‐NH₂(Al) is responsible for the observed catalytic activity. The developed synthetic procedure was also successful for the immobilisation of a Zhan catalyst.     

Mild and Selective Catalytic Hydrogenation of the C=C Bond in α,β‐Unsaturated Carbonyl Compounds Using Supported Palladium Nanoparticles

Chemoselective reduction of the C=C bond in a variety of α,β‐unsaturated carbonyl compounds using supported palladium nanoparticles is reported. Three different heterogeneous catalysts were compared using 1 atm of H₂: 1) nano‐Pd on a metal–organic framework (MOF: Pd⁰‐MIL‐101‐NH₂(Cr)), 2) nano‐Pd on a siliceous mesocellular foam (MCF: Pd⁰‐AmP‐MCF), and 3) commercially available palladium on carbon (Pd/C). Initial studies showed that the Pd@MOF and Pd@MCF nanocatalysts were superior in activity and selectivity compared to commercial Pd/C. Both Pd⁰‐MIL‐101‐NH₂(Cr) and Pd⁰‐AmP‐MCF were capable of delivering the desired products in very short reaction times (10–90 min) with low loadings of Pd (0.5–1 mol %). Additionally, the two catalytic systems exhibited high recyclability and very low levels of metal leaching.     

Sustainable Catalysis: Rational Pd Loading on MIL‐101Cr‐NH2 for More Efficient and Recyclable Suzuki–Miyaura Reactions

Palladium nanoparticles have been immobilized into an amino‐functionalized metal–organic framework (MOF), MIL‐101Cr‐NH₂, to form Pd@MIL‐101Cr‐NH₂. Four materials with different loadings of palladium have been prepared (denoted as 4‐, 8‐, 12‐, and 16 wt %Pd@MIL‐101Cr‐NH₂). The effects of catalyst loading and the size and distribution of the Pd nanoparticles on the catalytic performance have been studied. The catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier‐transform infrared (FTIR) spectroscopy, powder X‐ray diffraction (PXRD), N₂‐sorption isotherms, elemental analysis, and thermogravimetric analysis (TGA). To better characterize the palladium nanoparticles and their distribution in MIL‐101Cr‐NH₂, electron tomography was employed to reconstruct the 3D volume of 8 wt %Pd@MIL‐101Cr‐NH₂ particles. The pair distribution functions (PDFs) of the samples were extracted from total scattering experiments using high‐energy X‐rays (60 keV). The catalytic activity of the four MOF materials with different loadings of palladium nanoparticles was studied in the Suzuki–Miyaura cross‐coupling reaction. The best catalytic performance was obtained with the MOF that contained 8 wt % palladium nanoparticles. The metallic palladium nanoparticles were homogeneously distributed, with an average size of 2.6 nm. Excellent yields were obtained for a wide scope of substrates under remarkably mild conditions (water, aerobic conditions, room temperature, catalyst loading as low as 0.15 mol %). The material can be recycled at least 10 times without alteration of its catalytic properties.     

Dispersive magnetic solid‐phase extraction of phthalate esters from water samples and human plasma based on a nanosorbent composed of MIL‐101(Cr) metal–organic framework and magnetite nanoparticles before their determination by GC–MS

In this study, a magnetic metal–organic framework was synthesized simply and utilized in the dispersive magnetic solid‐phase extraction of five phthalate esters followed by their determination by gas chromatography with mass spectrometry. First, MIL‐101(Cr) was prepared hydrothermally in water medium without using highly corrosive hydrofluoric acid, utilizing an autoclave oven heat supply. Afterward, Fe₃O₄ nanoparticles were decorated into the matrix of MIL‐101(Cr) to fabricate magnetic MIL‐101 nanocomposite. The nanocomposite was characterized by various techniques. The parameters affecting dispersive magnetic solid‐phase extraction efficiency were optimized and obtained as: a sorbent amount of 15 mg; a sorption time of 20 min; an elution time of 5 min; NaCl concentration, 10% w/v; type and volume of the eluent 1 mL n‐hexane/acetone (1:1 v/v). Under the optimum conditions detection limits and linear dynamic ranges were achieved in the range of 0.08–0.15 and 0.5–200 μg/L, respectively. The intra‐ and interday RSD% values were obtained in the range of 2.5–9.5 and 4.6–10.4, respectively. Ultimately, the applicability of the method was successfully confirmed by the extraction and determination of the model analytes in water samples, and human plasma in the range of microgram per liter and satisfactory results were obtained.     

Incorporation of metal‐organic framework amino‐modified MIL‐101 into glycidyl methacrylate monoliths for nano LC separation

Metal‐organic frameworks consisting of amino‐modified MIL‐101(M: Cr, Al, and Fe) crystals have been synthesized and subsequently incorporated to glycidyl methacrylate monoliths to develop novel stationary phases for nano‐liquid chromatography. Two incorporation approaches of these materials in monoliths were explored. The metal‐organic framework materials were firstly attached to the pore surface through reaction of epoxy groups present in the parent glycidyl methacrylate‐based monolith. Alternatively, NH₂‐MIL‐101(M) were admixed in the polymerization mixture. Using short time UV‐initiated polymerization, monolithic beds with homogenously dispersed metal‐organic frameworks were obtained. The chromatographic performance of embedded UV‐initiated composites was demonstrated with separations of polycyclic aromatic hydrocarbons and non‐steroidal anti‐inflammatory drugs as test solutes. In particular, the incorporation of the NH₂‐MIL‐101(Al) into the organic polymer monoliths led to an increase in the retention of all the analytes compared to the parent monolith. The hybrid monolithic columns also exhibited satisfactory run‐to‐run and column‐to‐column reproducibility.     

Adsorption of antimony using amino-functionalized magnetic MIL-101(Cr): Optimization by response surface methodology

Amino-functionalized magnetic MIL-101(Cr) was prepared via a one-step solvothermal method, characterized, and applied in adsorptive Sb(III) removal. The effects of solution pH, adsorbent dosage, and coexisting substances on the adsorption of Sb(III) by MIL-101(Cr)–NH₂/MnFe₂O₄ were studied. The adsorption kinetics were analyzed using pseudo-first order, pseudo-second order, intraparticle diffusion, and Elovich models, while Freundlich and Langmuir isotherm models were used to fit the experimental data. The pseudo-second-order kinetic model provided the best fit for the kinetic data. The maximum adsorption capacity of MIL-101(Cr)–NH₂/MnFe₂O₄ for Sb(III) was 91.07 ​mg/g, as calculated using the Langmuir adsorption isotherm model. Thermodynamic analysis revealed that the adsorption of antimony onto MIL-101(Cr)–NH₂/MnFe₂O₄ is spontaneous and endothermic, while response surface optimization revealed that the optimal conditions for Sb(III) adsorption by MIL-101(Cr)–NH₂/MnFe₂O₄ are an adsorbent loading of 222.55 ​mg/L, a pH of 4.5, and a temperature of 294.59 ​K. The predicted adsorption capacity of MIL-101(Cr)–NH₂/MnFe₂O₄ for Sb(III) is only a 1.8% deviation from the actual value. Furthermore, MIL-101(Cr)–NH₂/MnFe₂O₄ exhibits strong magnetism, allowing it to be separated from wastewater using a magnet. Finally, a preliminary economic analysis showed that the cost of treating a ton wastewater containing 25 ​mg/L antimony using this composite would be 26.24 USD. Thus, MIL-101(Cr)–NH₂/MnFe₂O₄ is promising for treatment of Sb(III)-containing wastewater.     

Aptamer‐modified magnetic metal‐organic framework MIL‐101 for highly efficient and selective enrichment of ochratoxin A

A facile and efficient strategy is developed to modify aptamers on the surface of the magnetic metal‐organic framework MIL‐101 for the rapid magnetic solid‐phase extraction of ochratoxin A. To the best of our knowledge, this is the first attempt to create a robust aptamer‐modified magnetic MIL‐101 with covalent bonding for the magnetic separation and enrichment of ochratoxin A. The saturated adsorption of ochratoxin A by aptamer‐modified magnetic MIL‐101 was 7.9 times greater than that by magnetic metal‐organic framework MIL‐101 due to the former's high selective recognition as well as good stability. It could be used for extraction more than 12 times with no significant changes in the extraction efficiency. An aptamer‐modified magnetic MIL‐101‐based method of magnetic solid‐phase extraction combined with ultra high performance liquid chromatography with tandem mass spectrometry was developed for the determination of trace ochratoxin A with limit of detection of 0.067 ng/L. Ochratoxin A of 4.53–13.7 ng/kg was determined in corn and peanut samples. The recoveries were in the range 82.8–108% with a relative standard deviation (n = 5) of 4.5–6.5%. These results show that aptamer‐modified magnetic MIL‐101 exhibits selective and effective enrichment performance and have excellent potential for the analysis of ultra‐trace targets from complex matrices.     

The synthesis of metal–organic framework Al‐MIL‐53‐derived Brønsted acid catalyst and its application in the Mannich reaction

A metal–organic framework Al‐MIL‐53‐NH₂‐derived Brønsted acid catalyst (Al‐MIL‐53‐RSO₃H) has been synthesized employing a post‐synthetic modification strategy under mild conditions. The Al‐MIL‐53‐RSO₃H catalyst was successfully utilized in the nitro‐Mannich reaction taking advantage of its strong Brønsted acidity. Good to excellent yields of Mannich adducts were achieved for a variety of acylimine substrates in the presence of 0.1 mol% Al‐MIL‐53‐RSO₃H. Furthermore, the Al‐MIL‐53‐RSO₃H catalyst can be recycled five times without decreasing the yield and selectivity of Mannich adducts.     

Long‐Term Photostability in Terephthalate Metal–Organic Frameworks

Prolonged (weeks) UV/Vis irradiation under Ar of UiO‐66(Zr), UiO66 Zr‐NO₂, MIL101 Fe, MIL125 Ti‐NH₂, MIL101 Cr and MIL101 Cr(Pt) shows that these MOFs undergo photodecarboxylation of benzenedicarboxylate (BDC) linker in a significant percentage depending on the structure and composition of the material. Routine characterization techniques such as XRD, UV/Vis spectroscopy and TGA fail to detect changes in the material, although porosity and surface area change upon irradiation of powders. In contrast to BCD‐containing MOFs, zeolitic imidazolate ZIF‐8 does not evolve CO₂ or any other gas upon irradiation.     

Magnetic iron(III)‐based framework composites for the magnetic solid‐phase extraction of fungicides from environmental water samples

We adopted a facile hydrofluoric acid‐free hydro‐/solvothermal method for the preparation of four magnetic iron(III)‐based framework composites (MIL‐101@Fe₃O₄‐COOH, MIL‐101‐NH₂@Fe₃O₄‐COOH, MIL‐53@Fe₃O₄‐COOH, and MIL‐53‐NH₂@Fe₃O₄‐COOH). The obtained four magnetic iron(III)‐based framework composites were applied to magnetic separation and enrichment of the fungicides (prochloraz, myclobutanil, tebuconazole, and iprodione) from environmental samples before high‐performance liquid chromatographic analysis. MIL‐101‐NH₂@Fe₃O₄‐COOH showed more remarkable pre‐concentration ability for the fungicides as compared to the other three magnetic iron(III)‐based framework composites. The extraction parameters affecting enrichment efficiency including extraction time, sample pH, elution time, and the desorption solvent were investigated and optimized. Under the optimized conditions, the standard curve of correlation coefficients were all above 0.991, the limits of detection were 0.04–0.4 μg/L, and the relative standard deviations were below 10.2%. The recoveries of two real water samples ranged from 71.1–99.1% at the low spiking level (30 μg/L). Therefore, the MIL‐101‐NH₂@Fe₃O₄‐COOH composites are attractive for the rapid and efficient extraction of fungicides from environmental water samples.     

Simple magnetization of Fe3O4/MIL‐53(Al)‐NH2 for a rapid vortex‐assisted dispersive magnetic solid‐phase extraction of phenol residues in water samples

The present work describes a simple route to magnetize MIL‐53(Al)‐NH₂ sorbent for rapid extraction of phenol residues from environmental samples. To extend the applications and performances of the metal‐organic frameworks in the field of adsorption materials, we combined the properties of metal‐organic frameworks and magnetite to decrease the extraction time and simplify the extraction process as well. In this study, a simple and quick vortex‐assisted dispersive magnetic solid phase extraction method for the extraction of ten United States Environmental Protection Agency's priority phenols from water samples prior to analysis by high‐performance liquid chromatography with photodiode array detection was proposed. The developed method exhibits a rapid enrichment of the target analytes within 10 s for extraction and 10 s for desorption. Low detection limits of 1.8‐41.7 µg/L and quantitation limits of 6.0‐139.0 µg/L with the relative standard deviations for intra‐ and interday analyses less than 12% were achieved. Satisfactory recoveries in the range of 80‐111% with the relative standard deviations less than 11% demonstrated that Fe₃O₄/MIL‐53(Al)‐NH₂ is promising sorbent in the field of magnetic solid‐phase extraction for environmental samples.     

Synthesis,Water Adsorption,and Proton Conductivity of Solid‐Solution‐Type Metal–Organic Frameworks Al(OH)(bdc‐OH)x(bdc‐NH2)1−x

Mixed‐ligand metal–organic frameworks Al(bdc‐OH)_x(bdc‐NH₂)_1?x (H₂bdc‐NH₂=aminoterepthalic acid, H₂bdc‐OH=hydroxyterephthalic acid) were synthesized and their water adsorption behavior and proton conductivity were investigated. All obtained compounds were isostructural to MIL‐53 (MIL=Materials of Institut Lavoisier) according to XRD measurements under ambient humidity conditions, and were also found to be single phase across the whole mixing ratio from the XRD measurements under humidified conditions. This result clearly shows that all compounds are a solid‐solution‐type mixture of ligands. MIL‐53‐NH₂ adsorbs one water molecule per formula with humidification whereas MIL‐53‐OH adsorbs five water molecules. The mixing ratio of the ligands in Al(OH)(bdc‐OH)_x(bdc‐NH₂)_1?x affected the gate‐opening pressure for water adsorption and total water uptake. Proton conductivity of these compounds largely depends on the adsorbed amount of water, which indicates that the proton conductivity of these compounds depends strongly on the hydrogen‐bond network of the conducting media.     

Synthesis of chromene derivatives in the presence of mordenite zeolite/MIL‐101 (Cr) metal–organic framework composite as catalyst

In the present study, the synthesis of mordenite zeolite/MIL‐101(Cr) metal–organic framework (MOF) composite [MOR/MIL‐101(Cr)] using the ship in a bottle method was suggested. The properties of prepared composite and individual MOF and MOR zeolite were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption–desorption measurement, and thermogravimetric analysis (TGA). The XRD results indicated diffraction peaks for each compound (MOR and MOF) in composite. The SEM and TEM images showed the formation of plates MOR (with size of 2.5 × 3 μm) along with spherical particles MIL‐101. The Brunauer–Emmett–Teller results showed that the surface area of the composite was smaller than individual MOF and MOR zeolite. Based on TGA plots, the hybrid zeolite/MOF composite was more thermally stable compared with the isolated MIL‐101(Cr). The composite was functionalized by post‐synthetic modification to obtain acid–base bifunctionality (H‐MOR/MIL‐101‐ED) for the synthesis of chromene derivatives. The acidity from framework Al‐O(H)‐Si sites in MOR and basicity from amine groups in MIL‐101 were obtained by post‐synthetic modification.     

Elimination of 4‐chlorophenol in aqueous solution by the Novel Pd/MIL‐101(Cr)‐Hydrogen‐Accelerated catalytic fenton system

Excessive consumption of Fe (II) and massive generation of sludge containing Fe (III) from classic Fenton process remains a major obstacle for its poor recycling of Fe (III) to Fe (II). Therefore, the MHACF‐MIL‐101(Cr) system, by introducing H₂, Pd⁰ and MIL‐101(Cr) into Fenton reaction system, was developed at normal temperature and pressure. In this system, the reduction of Fe^III back to Fe^II by solid catalyst Pd/MIL‐101(Cr) for the storage and activation of H₂, was accelerated significantly by above 10‐fold and 5‐fold controlled with the H₂‐MIL‐101(Cr) system and H₂‐Pd⁰ system, respectively. However, the concentration of Fe (II) generated by the reduction of Fe (III) could not be detected with the only input of H₂ and without the addition of MOFs material. In addition, the apparent consumption of Fe (II) in MHACF‐MIL‐101(Cr) system was half of that in classical Fenton system, while more Fe (II) might be reused infinitely in fact. Accordingly, only trace amount of Fe (II) vs H₂O₂ concentration was needed and hydroxyl radicals through the detection of para‐hydroxybenzoic acid (p‐HBA) as the oxidative product of benzoic acid (BA) by·OH could be continuously generated for the effective degradation of 4‐chlorophenol(4‐CP). The effects of initial pH, concentration of 4‐CP, dosage of Fe²⁺, H₂O₂ and Pd/MIL‐101(Cr) catalyst, Pd content and H₂ flow were investigated, combined with systematic controlled experiments. Moreover, the robustness and morphology change of Pd/MIL‐101(Cr) were thoroughly analyzed. This study enables better understanding of the H₂‐mediated Fenton reaction enhanced by Pd/MIL‐101(Cr) and thus, will shed new light on how to accelerate Fe (III)/Fe (II) redox cycle and develop more efficient Fenton system.     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Evidence of Photoinduced Charge Separation in the Metal–Organic Framework MIL‐125(Ti)‐NH2

Herein, we describe the photochemical behavior of the porous metal–organic framework MIL‐125(Ti)‐NH₂, built up from cyclic Ti₈O₈(OH)₄ oxoclusters and 2‐aminoterephthalate ligands. While MIL‐125(Ti)‐NH₂ does not emit upon excitation at 420 nm, laser flash photolyses of dry samples (diffuse reflectance) or aqueous suspensions (transmission) of the solid have allowed detecting a transient characterized by a continuous absorption from 390 to 820 nm decaying in the sub‐millisecond timescale, which is quenched by oxygen. This transient has been attributed to the charge‐separation state. Firm evidence for this assignment was obtained by lamp irradiation of aqueous suspensions of MIL‐125(Ti)‐NH₂ in the presence of electron‐donor (N,N,N′N′‐tetramethyl‐p‐phenylenediamine) or electron‐acceptor (methylviologen) probe molecules, which has allowed the visual detection of the corresponding radical ions, in agreement with the occurrence of photoinduced charge separation in MIL‐125(Ti)‐NH₂.     

Nanoscale Metal–Organic Framework–Hemoglobin Conjugates

A metal–organic framework (MOF)–protein conjugate, NH₂‐MIL‐125(Ti)‐hemoglobin [MIL‐125(Ti)‐Hb], was synthesized by a covalent postmodification strategy. The crystalline structure was maintained after chemical and protein modification. The content of grafted Hb was tuned by the stoichiometric ratio and reached 50 wt % if the mass ratio of MIL‐125(Ti)/Hb was 1:1.25 in the feed. The oxygen‐transporting capacity of grafted Hb was kept, and the P₅₀ (the half O₂ pressure saturated with O₂) and Hill coefficients of the MIL‐125(Ti)‐Hb conjugate were found to be 22.9 mm Hg and 2.35, respectively, which are close to the respective values of free Hb. All the results indicate that the MIL‐125(Ti)‐Hb conjugate could be potentially used as an oxygen carrier.