Nanoscale Metal-Organic Frameworks as a Photoluminescent Platform for Bioimaging and Biosensing Applications.

The tracking of nanomedicines in their concentration and location inside living systems has a pivotal effect on the understanding of the biological processes, early-stage diagnosis, and therapeutic monitoring of diseases. Nanoscale metal-organic frameworks (nano MOFs) possess high surface areas, definite structure, regulated optical properties, rich functionalized sites, and good biocompatibility that allow them to excel in a wide range of biomedical applications. Controllable syntheses and functionalization endow nano MOFs with better properties as imaging agents and sensing units for the diagnosis and treatment of diseases. This minireview summarizes the tunable synthesis strategies of nano MOFs with controllable size, shape, and regulated luminescent performance, and pinpoints their recent advanced applications as optical elements in bioimaging and biosensing. The current limitations and future development directions of nano MOF-contained materials in bioimaging and biosensing applications are also discussed, aiming to expand the biological applications of nano MOF-based nanomedicine and facilitate their production or clinical translation.

Orthogonal Postsynthetic Copolymerization of Hydrogen-Bonded Organic Frameworks into a PolyHOF Membrane.

Hydrogen-bonded organic frameworks (HOFs) have shown promise in various fields; however, the construction of HOF/polymer hybrid membranes that can maintain both structural and functional integrity remains challenging. In this study, we here fabricated a new HOF (HOF-50) with reserved polymerizable allyl group via charge-assisted H-bonds between the carboxylate anion and amidinium, and subsequently copolymerized the HOF with monomers to construct a covalently bonded HOF/polymer hybrid (polyHOF) membrane. The resulting polyHOF membrane not only exhibits customizable mechanical properties and extreme stability, but also shows an exceptional ratiometric luminescent temperature-sensing function with very high sensitivity and visibility even when the lanthanide content is two orders of magnitude lower than that of the reported mixed-lanthanide metal-organic frameworks (MOFs) and lanthanide-doped covalent organic frameworks (COFs). This orthogonal postsynthesis copolymerization strategy may provide a general approach for preparing covalently connected HOF/polymer hybrid membranes for diverse applications.

Exploring Multifunctional Hydrogen-Bonded Organic Framework Materials.

Hydrogen-bonded organic framework (HOF) materials have provided a new dimension and bright promise as a new platform for developing multifunctional materials. They can be readily self-assembled from their corresponding organic molecules with diverse functional sites such as carboxylic acid and amine groups for their hydrogen bonding and aromatic ones for their weak π···π interactions to stabilize the frameworks. Compared with those established porous materials such as zeolites, metal-organic frameworks (MOFs), and covalent-organic frameworks (COFs), it is much more difficult to stabilize HOFs and thus establish their permanent porosities given the fact that hydrogen bonds are typically weaker than ionic, coordination, and covalent bonds. But it provides the uniqueness of HOF materials in which they can be easily recovered and regenerated through simple recrystallization. HOF materials can also be easily and straightforwardly processed and very compatible with the biomolecules, making them potentially very useful materials for industrial and biomedical applications. The reversible and weak bonding nature of the hydrogen bonds can be readily utilized to construct flexible porous HOF materials in which we can tune the temperature and pressure to control their porosities and, thus, their diverse applications, for example, on gas separations, gas storage, drug delivery, and sensing. Some specific organic functional groups are quite directional for the hydrogen bond formations; for example, carboxylic acid prefers to form a directional dimer, which has enabled us to readily construct reticular porous HOF materials whose pores can be systematically tuned. In this Account, we outline our journey of exploring this new type of porous material by establishing one of the first porous HOFs in 2011 and thus developing its diverse applications. We have been able to use organic molecules with different functional sites, including 2,4-diaminotriazine (DAT), carboxylic acid (COOH), aldehyde (CHO), and cyano (CN), to construct porous HOFs. Through tuning the pore sizes, introducing specific binding sites, and making use of the framework flexibility, we have realized a series of HOF materials for the gas separations of C2H2/C2H4, C2H4/C2H6, C3H6/C3H8, C2H2/CO2, CO2/N2, and Xe/Kr and enantioselective separation of alcohols. To make use of optically active organic molecules, we have developed HOF materials for their luminescent sensing and optical lasing. Our research endeavors on multifunctional HOF materials have initiated extensive research in this emerging research topic among chemistry and materials sciences communities. We foresee that not only many more HOF materials will be developed but novel functions will be fulfilled beyond our imaginations soon.

Metformin promotes bacterial surface aggregation by inhibiting the swimming motility of flagellated Escherichia coli.

The antiglycemic drug metformin, which is widely prescribed as a first-line drug for the treatment of type 2 diabetes, has become a concern for emerging pollutants in natural ecosystems. However, its effects on bacterial swimming motility remain unclear. In this study, we showed that metformin promotes bacterial surface aggregation by tracking swimming and by measuring the density distribution of Escherichia coli cultured with metformin near a surface in a homogeneous environment. Flagella are essential for the promotion of bacterial surface aggregation by metformin. Swimming motility, which is mediated by flagella, determines bacterial surface aggregation. The promotion of bacterial surface aggregation by metformin is caused by a reduction in swimming motility, which is governed by a decrease in the proton motive force. Our results reveal that metformin has a pronounced effect on flagellated bacterial motility associated with surface sensing and aggregation.

A Microporous Metal-Organic Framework with Unique Aromatic Pore Surfaces for High Performance C2 H6 /C2 H4 Separation.

Developing adsorptive separation processes based on C2 H6 -selective sorbents to replace energy-intensive cryogenic distillation is a promising alternative for C2 H4 purification from C2 H4 /C2 H6 mixtures, which however remains challenging. During our studies on two isostructural metal-organic frameworks (Ni-MOF 1 and Ni-MOF 2), we found that Ni-MOF 2 exhibited significantly higher performance for C2 H6 /C2 H4 separation than Ni-MOF-1, as clearly established by gas sorption isotherms and breakthrough experiments. Density-Functional Theory (DFT) studies showed that the unblocked unique aromatic pore surfaces within Ni-MOF 2 induce more and stronger C-H⋅⋅⋅π with C2 H6 over C2 H4 while the suitable pore spaces enforce its high C2 H6 uptake capacity, featuring Ni-MOF 2 as one of the best porous materials for this very important gas separation. It generates 12 L kg-1 of polymer-grade C2 H4 product from equimolar C2 H6 /C2 H4 mixtures at ambient conditions.

Metal-Organic Framework Based Hydrogen-Bonding Nanotrap for Efficient Acetylene Storage and Separation.

The removal of carbon dioxide (CO2) from acetylene (C2H2) is a critical industrial process for manufacturing high-purity C2H2. However, it remains challenging to address the tradeoff between adsorption capacity and selectivity, on account of their similar physical properties and molecular sizes. To overcome this difficulty, here we report a novel strategy involving the regulation of a hydrogen-bonding nanotrap on the pore surface to promote the separation of C2H2/CO2 mixtures in three isostructural metal-organic frameworks (MOFs, named MIL-160, CAU-10H, and CAU-23, respectively). Among them, MIL-160, which has abundant hydrogen-bonding acceptors as nanotraps, can selectively capture acetylene molecules and demonstrates an ultrahigh C2H2 storage capacity (191 cm3 g-1, or 213 cm3 cm-3) but much less CO2 uptake (90 cm3 g-1) under ambient conditions. The C2H2 adsorption amount of MIL-160 is remarkably higher than those for the other two isostructural MOFs (86 and 119 cm3 g-1 for CAU-10H and CAU-23, respectively) under the same conditions. More importantly, both simulation and experimental breakthrough results show that MIL-160 sets a new benchmark for equimolar C2H2/CO2 separation in terms of the separation potential (Δqbreak = 5.02 mol/kg) and C2H2 productivity (6.8 mol/kg). In addition, in situ FT-IR experiments and computational modeling further reveal that the unique host-guest multiple hydrogen-bonding interaction between the nanotrap and C2H2 is the key factor for achieving the extraordinary acetylene storage capacity and superior C2H2/CO2 selectivity. This work provides a novel and powerful approach to address the tradeoff of this extremely challenging gas separation.

A Flexible Hydrogen-Bonded Organic Framework Constructed from a Tetrabenzaldehyde with a Carbazole N-H Binding Site for the Highly Selective Recognition and Separation of Acetone.

Rational design of hydrogen-bonded organic frameworks (HOFs) with multiple functionalities is highly sought after but challenging. Herein, we report a multifunctional HOF (HOF-FJU-2) built from 4,4',4'',4'''-(9H-carbazole-1,3,6,8-tetrayl)tetrabenzaldehyde molecule with tetrabenzaldeyde for their H bonding interactions and carbazole N-H site for its specific recognition of small molecules. The Lewis acid N-H sites allow HOF-FJU-2 facilely separate acetone from its mixture with another solvent like methanol with smaller pKa value. The donor (D)-π-acceptor (A) aromatic nature of the organic building molecule endows this HOF with solvent dependent luminescent/chromic properties, so the column acetone/methanol separation on HOF-FJU-2 can be readily visualized.

Second-Sphere Interaction Promoted Turn-On Fluorescence for Selective Sensing of Organic Amines in a TbIII -based Macrocyclic Framework.

Guided by a second-sphere interaction strategy, we fabricated a Tb(III)-based metal-organic framework (MMCF-4) for turn-on sensing of methyl amine with ultra-low detection limit and high turn-on efficiency. MMCF-4 features lanthanide nodes shielded in a nonacoordinate geometry along with secondary coordination spheres that are densely populated with H-bond interacting sites. Nonradiative routes were inhibited by binding-induced rigidification of the ligand on the second coordination sphere, resulting in luminescence amplification. Such remote interacting mechanism involved in the turn-on sensing event was confirmed by single-crystal X-ray diffraction and molecular dynamic simulation studies. The design of both primary and secondary coordination spheres of Tb(III) enabled the first turn-on sensing of organic amines in aqueous conditions. Our work suggests a promising strategy for high-performance turn-on sensing for Ln-MOFs and luminous materials driven by other metal chromophores.

Integrating the Pillared-Layer Strategy and Pore-Space Partition Method to Construct Multicomponent MOFs for C2H2/CO2 Separation.

Introducing multiclusters and multiligands (mm) in a well-defined array will greatly increase the diversity of metal-organic frameworks (MOFs). Here, a series of porous mm-MOFs constructed from a pillared-layer and pore-space partition (PL-PSP) have been achieved. FJU-6 with {Co3}-cluster-based sheets and {Co6}-cluster-based pillars exhibits new (3,9,12)-connected llz topology. By using the substituted analogues of the ligands and metal ions, seven isoreticular mm-MOFs (FJU-6-X, X = PTB, TATB, Me-INA, F-INA, NDC, BrBDC, Ni) have been synthesized with the adjustable BET surface areas ranging from 731 to 1306 m2/g as well as the adsorption capacity of CO2 increasing by 77%. The C2H2/CO2 mixture can be effectively separated in the breakthrough experiments in the fixed bed filled with solid FJU-6-TATB at ambient temperature. In all, integrating pillared-layer strategy and pore-space partitioning is effective at constructing mm-MOFs with multivariate environments for the optimization of gas adsorption and separation.

Isoreticular Microporous Metal-Organic Frameworks for Carbon Dioxide Capture.

The isoreticular principle has been applied to construct two copper metal-organic framework (MOF) analogues with different porosities for the adsorptive capture of CO2 from N2 and CH4 at 1 atm and 298 K. By using a 4-substituted isophthalate linker with a bulky nitro group, the microporous MOF [Cu(BDC-NO2)(DMF)] (UTSA-93 or CuBDC-NO2; H2BDC-NO2 = 4-nitroisophthalic acid and DMF = N,N'-dimethylformamide) has been synthesized with mot topology, showing a compact pore structure with a size of 6.0 × 7.0 Å2 in contrast to that of 6.9 × 8.5 Å2 in the prototypical MOF with a bromo group. The optimized pore structure allows the nitro-functionalized MOF to capture CO2 with a higher capacity of about 2.40 mmol g-1 under ambient conditions, in contrast to 1.08 mmol g-1 in the bromo-functionalized analogue. The adsorption selectivity of CuBDC-NO2-a for a CO2/N2 (15:85) mixture (28) under ambient conditions is also higher than that of the bromo-substituted prototype (25) and comparable with those of several MOF materials. Moreover, dynamic breakthrough experiments of the nitro-functionalized MOF have been performed to illustrate its separation potential toward a CO2/N2 mixture.

Solvent-Assisted Modification to Enhance Proton Conductivity and Water Stability in Metal Phosphonates.

Although proton-conductive metal phosphonates with well-defined structure offer a favorable platform for exploring their structure-property relationship, investigating of the synergic effect of phosphonate groups and functional moieties on proton conduction is rare. In this work, we have synthesized two new copper phosphonates, [Cu(4-cppH)(4,4'-bipy)(H2O)3] (FJU-80) and [Cu(4-cppH)(4,4'-bipy)]·H2O·DMF (FJU-81), by the method of solvent-assisted modification, giving a 1D metal coordination polymer and a 3D metal open framework, respectively. Single-crystal X-ray diffraction shows that FJU-80 is full of hydrogen-bonding sites contributed from the improved synergic effect of phosphonate groups, carboxylate groups, and coordinated water molecules, thereby facilitating continuous hydrogen-bonding networks, whereas FJU-81 only has discrete hydrogen-bonding fragments. Powder X-ray diffraction and impedance analyses confirm that FJU-80 possesses higher water stability as well as improved proton conductivity, indicating that solvent-assisted modification is effective in increasing the hydrogen-bonding sites from phosphonate groups and functional moieties and then realizing facile proton transfer.

A Robust Mixed-Lanthanide PolyMOF Membrane for Ratiometric Temperature Sensing.

Temperature sensors play a significant role in biology, chemistry, and engineering, especially those that can work accurately in a noninvasive manner. We adopted a photoinduced post-synthetic copolymerization strategy to realize a membranous ratiometric luminescent thermometer based on the emissions of two lanthanide ions. This novel mixed-lanthanide polyMOF membrane exhibits not only the integrity and temperature sensing behaviour of the Ln-MOF powder but also excellent mechanical properties, such as flexibility, elasticity, and processability. Moreover, the polyMOF membrane shows remarkable stability under harsh conditions, including high humidity, strong acid and alkali (pH 0-14), which allowed the mapping of temperature distributions in extreme circumstances. This work highlights a simple strategy for polyMOF membrane formation and pushes forward the further practical application of Ln-MOF-based luminescent thermometers in various fields and conditions.

Pore Space Partition within a Metal-Organic Framework for Highly Efficient C2H2/CO2 Separation.

The pore space partition (PSP) approach has been employed to realize a novel porous MOF (FJU-90) with dual functionalities for the challenging C2H2/CO2 separation under ambient conditions. By virtue of a triangular ligand (Tripp = 2,4,6-tris(4-pyridyl)pyridine), the cylindrical channels in the original FJU-88 have been partitioned into uniformly interconnected pore cavities, leading to the dramatically reduced pore apertures from 12.0 × 9.4 to 5.4 × 5.1 Å2. Narrowing down the pore sizes, the resulting activated FJU-90a takes up a very large amount of C2H2 (180 cm3 g-1) but much less of CO2 (103 cm3 g-1) at 298 K and 1 bar, demonstrating it to be the best porous MOF material for this C2H2/CO2 (50%:50%) separation in terms of the C2H2 gravimetric productivity. IAST calculations, molecular modeling studies, and simulated and experimental breakthrough experiments comprehensively demonstrate that the pore space partition strategy is a very powerful approach to constructing MOFs with dual functionality for challenging gas separation.

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.

Metal-Organic Framework with Rich Accessible Nitrogen Sites for Highly Efficient CO2 Capture and Separation.

A novel microporous metal-organic framework (FJU-44), with abundant accessible nitrogen sites on its internal surface, was constructed from the tetrapodal tetrazole ligand tetrakis(4-tetrazolylphenyl)ethylene (H4TTPE) and copper chloride. Notably, the CO2 uptake capacity (83.4 cm3/g, at 273 K and 1 bar) in the activated FJU-44a is higher than most of tetrazolate-containing MOF materials. Particularly, FJU-44a exhibits superior adsorption selectivity of CO2/N2 (278-128) and CO2/CH4 (44-16), which is comparable to some well-known CO2 capture materials. Furthermore, the fixed-bed breakthrough experiment indicates that the postcombustion flue gas flow over a packed column with FJU-44a adsorbents can be effectively separated.

Loading Photochromic Molecules into a Luminescent Metal-Organic Framework for Information Anticounterfeiting.

Stimuli-responsive photoluminescent materials have attracted considerable attention owing to their potential applications in security protection because the information recorded directly in materials with static luminescent outputs are usually visible under either ambient or UV light. Herein, we realize reversible information anticounterfeiting by loading a photoswitchable diarylethene derivative into a lanthanide metal-organic framework (MOF). Light triggers the open- and closed-form isomerization of the diarylethene unit, which respectively regulates the inactivation and activation of the photochromic FRET process between the diarylethene acceptor and lanthanide donor, resulting in reversible luminescence on-off switching of the lanthanide emitting center in the MOF host. This photoresponsive host-guest system allows for reversible multiple information pattern visible/invisible transformation by simply alternating the exposure to UV and visible light.

Robustness, Selective Gas Separation, and Nitrobenzene Sensing on Two Isomers of Cadmium Metal-Organic Frameworks Containing Various Metal-O-Metal Chains.

Poor stability has been one of the major difficulties affecting to the practical application of metal-organic frameworks (MOFs). In this work, we obtained two 3D structurally isomeric Cd-MOFs, {[Cd6(NH2Me2)2(PTB)4(HCOO)2(H2O)]·(DMF)13·(H2O)4} n (FJU-35) and {[Cd6(NH2Me2)2(PTB)4(HCOO)2]·(DMF)6·(H2O)2} n (FJU-36) (H3PTB = pyridine-2,4,6-tribenzoic acid) containing different CdII-O-CdII chains by varying the addition agents. FJU-35 with coordinated solvent and formate in asymmetric µ3-η1:η2 coordination mode within the CdII-O-CdII chains is vulnerable to external attacks and is apt to collapse after activation, while FJU-36 with no coordinated solvent in the CdII-O-CdII chains but fully protected by the carboxylates from the ligands and the symmetric formate in the coordination mode µ3-η2:η2 is stable, and its activated sample shows efficient separation of C2H2/CH4 and C2H2/CO2 mixtures. Conversely, FJU-35 with more vulnerability is more sensitive to the detection of nitrobenzene than FJU-36.

Straightforward Loading of Imidazole Molecules into Metal-Organic Framework for High Proton Conduction.

A one-step straightforward strategy has been developed to incorporate free imidazole molecules into a highly stable metal-organic framework (NENU-3, ([Cu12(BTC)8(H2O)12][HPW12O40])·Guest). The resulting material Im@(NENU-3) exhibits a very high proton conductivity of 1.82 × 10-2 S cm-1 at 90% RH and 70 °C, which is significantly higher than 3.16 × 10-4 S cm-1 for Im-Cu@(NENU-3a) synthesized through a two-step approach with mainly terminal bound imidazole molecules inside pores. Single crystal structure reveals that imidazole molecules in Im-Cu@(NENU-3a) isolate lattice water molecules and then block proton transport pathway, whereas high concentration of free imidazole molecules within Im@(NENU-3) significantly facilitate successive proton-hopping pathways through formation of hydrogen bonded networks.

Microporous Metal-Organic Framework Stabilized by Balanced Multiple Host-Couteranion Hydrogen-Bonding Interactions for High-Density CO2 Capture at Ambient Conditions.

Microporous metal organic frameworks (MOFs) show promising application in several fields, but they often suffer from the weak robustness and stability after the removal of guest molecules. Here, three isostructural cationic metal-organic frameworks {[(Cu4Cl)(cpt)4(H2O)4]·3X·4DMAc·CH3OH·5H2O} (FJU-14, X = NO3, ClO4, BF4; DMAc = N,N'-dimethylacetamide) containing two types of polyhedral nanocages, one octahedron, and another tetrahedron have been synthesized from bifunctional organic ligands 4-(4H-1,2,4-triazol-4-yl) benzoic acid (Hcpt) and various copper salts. The series of MOFs FJU-14 are demonstrated as the first examples of the isostructural MOFs whose robustness, thermal stability, and CO2 capacity can be greatly improved via rational modulation of counteranions in the tetrahedral cages. The activated FJU-14-BF4-a containing BF4(-) anion can take CO2 of 95.8 cm(3) cm(-3) at ambient conditions with an adsorption enthalpy only of 18.8 kJ mol(-1). The trapped CO2 density of 0.955 g cm(-3) is the highest value among the reported MOFs. Dynamic fixed bed breakthrough experiments indicate that the separation of CO2/N2 mixture gases through a column packed with FJU-14-BF4-a solid can be efficiently achieved. The improved robustness and thermal stability for FJU-14-BF4-a can be attributed to the balanced multiple hydrogen-bonding interactions (MHBIs) between the BF4(-) counteranion and the cationic skeleton, while the high-density and low-enthalpy CO2 capture on FJU-14-BF4-a can be assigned to the multiple-point interactions between the adsorbate molecules and the framework as well as with its counteranions, as proved by single-crystal structures of the guest-free and CO2-loaded FJU-14-BF4-a samples.

40-Fold Enhanced Intrinsic Proton Conductivity in Coordination Polymers with the Same Proton-Conducting Pathway by Tuning Metal Cation Nodes.

Three isostructural imidazole-cation-templated metal phosphates (FJU-25) are the first examples to demonstrate that the tuning of metal cation nodes can be an efficient strategy to significantly improve the proton conductivity without changing the structure of the proton-conducting pathway.