Chemiluminescent and chemiluminescence resonance energy transfer (CRET) detection of DNA, metal ions, and aptamer-substrate complexes using hemin/G-quadruplexes and CdSe/ZnS quantum dots

Nucleic acid subunits consisting of fragments of the horseradish peroxidase (HRP)-mimicking DNAzyme and aptamer domains against ATP or sequences recognizing Hg(2+) ions self-assemble, in the presence of ATP or Hg(2+), into the active hemin-G-quadruplex DNAzyme structure. The DNAzyme-generated chemiluminescence provides the optical readout for the sensing events. In addition, the DNAzyme-stimulated chemiluminescence resonance energy transfer (CRET) to CdSe/ZnS quantum dots (QDs) is implemented to develop aptamer or DNA sensing platforms. The self-assembly of the ATP-aptamer subunits/hemin-G-quadruplex DNAzyme, where one of the aptamer subunits is functionalized with CdSe/ZnS QDs, leads to the CRET signal. Also, the functionalization of QDs with a hairpin nucleic acid that includes the G-quadruplex sequence in a 'caged' configuration is used to analyze DNA. The opening of the hairpin structure by the target DNA assembles the hemin-G-quadruplex DNAzyme that stimulates the CRET signal. By the application of three different sized QDs functionalized with different hairpins, the multiplexed analysis of three different DNA targets is demonstrated by the generation of three different CRET luminescence signals.     

Free-standing metal–organic framework (MOF) monolayers by self-assembly of polymer-grafted nanoparticles

We report a general method for the synthesis of free-standing, self-assembled MOF monolayers (SAMMs) at an air–water interface using polymer-brush coated MOF nanoparticles. UiO-66, UiO-66-NH₂, and MIL-88B-NH₂ were functionalized with a catechol-bound chain-transfer agent (CTA) to graft poly(methyl methacrylate) (PMMA) from the surface of the MOF using reversible addition-fragmentation chain transfer polymerization (RAFT). The polymer-coated MOFs were self-assembled at the air–water interface into monolayer films ∼250 nm thick and capable of self-supporting at a total area of 40 mm². Mixed-particle films were prepared through the assembly of MOF mixtures, while multilayer films were achieved through sequential transfer of the monolayers to a glass slide substrate. This method offers a modular and generalizable route to fabricate thin-films with inherent porosity and sub-micron thickness composed of a variety of MOF particles and functionalities.

We report a general method for the synthesis of free-standing, self-assembled MOF monolayers (SAMMs) at an air–water interface using polymer-brush coated MOF nanoparticles.     

Single-step synthesis and interface tuning of core–shell metal–organic framework nanoparticles

Control over the spatial distribution of components in metal–organic frameworks has potential to unlock improved performance and new behaviour in separations, sensing and catalysis. We report an unprecedented single-step synthesis of multi-component metal–organic framework (MOF) nanoparticles based on the canonical ZIF-8 (Zn) system and its Cd analogue, which form with a core–shell structure whose internal interface can be systematically tuned. We use scanning transmission electron microscopy, X-ray energy dispersive spectroscopy and a new composition gradient model to fit high-resolution X-ray diffraction data to show how core–shell composition and interface characteristics are intricately controlled by synthesis temperature and reaction composition. Particle formation is investigated by in situ X-ray diffraction, which reveals that the spatial distribution of components evolves with time and is determined by the interplay of phase stability, crystallisation kinetics and diffusion. This work opens up new possibilities for the control and characterisation of functionality, component distribution and interfaces in MOF-based materials.

Core–shell metal–organic framework nanoparticles have been synthesised in which the internal interface and distribution of components is found to be highly tunable using simple variations in reaction conditions.     

Highly efficient Förster resonance energy transfer between an emissive tetraphenylethylene-based metal–organic cage and the encapsulated dye guest

The host–guest strategy presents an ideal way to achieve efficient Förster resonance energy transfer (FRET) by forcing close proximity between an energy donor and acceptor. Herein, by encapsulating the negatively charged acceptor dyes eosin Y (EY) or sulforhodamine 101 (SR101) in the cationic tetraphenylethene-based emissive cage-like host donor Zn-1, host–guest complexes were formed that exhibit highly efficient FRET. The energy transfer efficiency of Zn-1⊃EY reached 82.4%. To better verify the occurrence of the FRET process and make full use of the harvested energy, Zn-1⊃EY was successfully used as a photochemical catalyst for the dehalogenation of α-bromoacetophenone. Furthermore, the emission color of the host–guest system Zn-1⊃SR101 could be adjusted to exhibit bright white-light emission with the CIE coordinates (0.32, 0.33). This work details a promising approach to enhance the efficiency of the FRET process by the creation of a host–guest system between the cage-like host and dye acceptor, thus serving as a versatile platform for mimicking natural light-harvesting systems.

Highly efficient Förster resonance energy transfer was realized between an emissive metal–organic cage and encapsulated dyes through the close space distance forced by host–guest interaction.     

Recent progress in metal–organic framework/graphene-derived materials for energy storage and conversion: design,preparation, and application

Graphene or chemically modified graphene, because of its high specific surface area and abundant functional groups, provides an ideal template for the controllable growth of metal–organic framework (MOF) particles. The nanocomposite assembled from graphene and MOFs can effectively overcome the limitations of low stability and poor conductivity of MOFs, greatly widening their application in the field of electrochemistry. Furthermore, it can also be utilized as a versatile precursor due to the tunable structure and composition for various derivatives with sophisticated structures, showing their unique advantages and great potential in many applications, especially energy storage and conversion. Therefore, the related studies have been becoming a hot research topic and have achieved great progress. This review summarizes comprehensively the latest methods of synthesizing MOFs/graphene and their derivatives, and their application in energy storage and conversion with a detailed analysis of the structure–property relationship. Additionally, the current challenges and opportunities in this field will be discussed with an outlook also provided.

This review summarizes comprehensively the latest methods of synthesizing MOFs/graphene and their derivatives, and their application in energy storage and conversion with a detailed analysis of the structure–property relationship.     

Crystallographic characterization of the metal–organic framework Fe2(bdp)3 upon reductive cation insertion

Precisely locating extra-framework cations in anionic metal–organic framework compounds remains a long-standing, yet crucial, challenge for elucidating structure–performance relationships in functional materials. Single-crystal X-ray diffraction is one of the most powerful approaches for this task, but single crystals of frameworks often degrade when subjected to post-synthetic metalation or reduction. Here, we demonstrate the growth of sizable single crystals of the robust metal–organic framework Fe₂(bdp)₃ (bdp²⁻ = benzene-1,4-dipyrazolate) and employ single-crystal-to-single-crystal chemical reductions to access the solvated framework materials A₂Fe₂(bdp)₃·yTHF (A = Li⁺, Na⁺, K⁺). X-ray diffraction analysis of the sodium and potassium congeners reveals that the cations are located near the center of the triangular framework channels and are stabilized by weak cation–π interactions with the framework ligands. Freeze-drying with benzene enables isolation of activated single crystals of Na_0.5Fe₂(bdp)₃ and Li₂Fe₂(bdp)₃ and the first structural characterization of activated metal–organic frameworks wherein extra-framework alkali metal cations are also structurally located. Comparison of the solvated and activated sodium-containing structures reveals that the cation positions differ in the two materials, likely due to cation migration that occurs upon solvent removal to maximize stabilizing cation–π interactions. Hydrogen adsorption data indicate that these cation–framework interactions are sufficient to diminish the effective cationic charge, leading to little or no enhancement in gas uptake relative to Fe₂(bdp)₃. In contrast, Mg_0.85Fe₂(bdp)₃ exhibits enhanced H₂ affinity and capacity over the non-reduced parent material. This observation shows that increasing the charge density of the pore-residing cation serves to compensate for charge dampening effects resulting from cation–framework interactions and thereby promotes stronger cation–H₂ interactions.

Single-crystal X-ray diffraction reveals structural influences on gas adsorption properties in anionic metal–organic frameworks.     

Backbonding contributions to small molecule chemisorption in a metal–organic framework with open copper(i) centers

Metal–organic frameworks are promising materials for applications such as gas capture, separation, and storage, due to their ability to selectively adsorb small molecules. The metal–organic framework Cu^I-MFU-4l, which contains coordinatively unsaturated copper(i) centers, can engage in backbonding interactions with various small molecule guests, motivating the design of frameworks that engage in backbonding and other electronic interactions for highly efficient and selective adsorption. Here, we examine several gases expected to bind to the open copper(i) sites in Cu^I-MFU-4l via different electronic interactions, including σ-donation, π-backbonding, and formal electron transfer. We show that in situ Cu L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy can elucidate π-backbonding by directly probing excitations to unoccupied backbonding orbitals with Cu d-character, even for gases that participate in other dominant interactions, such as ligand-to-metal σ-donation. First-principles calculations based on density functional theory and time-dependent density functional theory additionally reveal the backbonding molecular orbitals associated with these spectroscopic transitions. The energies of the transitions correlate with the energy levels of the isolated small molecule adsorbates, and the transition intensities are proportional to the binding energies of the guest molecules within Cu^I-MFU-4l. By elucidating the molecular and electronic structure origins of backbonding interactions between electron rich metal centers in metal–organic frameworks and small molecule guests, it is possible to develop guidelines for further molecular-level design of solid-state adsorbents for energy-efficient separations of relevance to industry.

In situ near edge X-ray absorption fine structure spectroscopy directly probes unoccupied states associated with backbonding interactions between the open metal site in a metal–organic framework and various small molecule guests.     

A switchable sensor and scavenger: detection and removal of fluorinated chemical species by a luminescent metal–organic framework

Fluorosis has been regarded as a worldwide disease that seriously diminishes the quality of life through skeletal embrittlement and hepatic damage. Effective detection and removal of fluorinated chemical species such as fluoride ions (F⁻) and perfluorooctanoic acid (PFOA) from drinking water are of great importance for the sake of human health. Aiming to develop water-stable, highly selective and sensitive fluorine sensors, we have designed a new luminescent MOF In(tcpp) using a chromophore ligand 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine (H₄tcpp). In(tcpp) exhibits high sensitivity and selectivity for turn-on detection of F⁻ and turn-off detection of PFOA with a detection limit of 1.3 μg L⁻¹ and 19 μg L⁻¹, respectively. In(tcpp) also shows high recyclability and can be reused multiple times for F⁻ detection. The mechanisms of interaction between In(tcpp) and the analytes are investigated by several experiments and DFT calculations. These studies reveal insightful information concerning the nature of F⁻ and PFOA binding within the MOF structure. In addition, In(tcpp) also acts as an efficient adsorbent for the removal of F⁻ (36.7 mg g⁻¹) and PFOA (980.0 mg g⁻¹). It is the first material that is not only capable of switchable sensing of F⁻ and PFOA but also competent for removing the pollutants via different functional groups.

A robust In-MOF, In(tcpp), demonstrates sensitive detection of the fluorinated chemical species F⁻ and PFOA via distinctly different luminescence signal change, and effective adsorption and removal of both species from aqueous solution.     

Oxidation reactions catalysed by molybdenum(VI) complexes grafted on UiO‐66 metal–organic framework as an elegant nanoreactor

A heterogeneous catalyst was synthesized by immobilizing Mo(CO)₃ in a UiO‐66 metal–organic framework. The benzene ring of the organic linker in UiO‐66 was modified via liquid‐phase deposition of molybdenum hexacarbonyl, Mo(CO)₆, as starting precursor to form the (arene)Mo(CO)₃ species inside the framework. The structure of this catalyst was characterized using X‐ray diffraction, and chemical integrity was confirmed using Fourier transform infrared and diffuse reflectance UV–visible spectroscopic methods. The metal content was analysed with inductively coupled plasma. Field emission scanning electron microscopy was used to measure particle size and N₂ adsorption measurements to characterize the specific surface area. This catalytic system was efficiently applied for epoxidation of alkenes and oxidation of sulfides. The Mo‐containing metal–organic framework was reused several times without any appreciable loss of its efficiency.     

Quantification of the mixed-valence and intervalence charge transfer properties of a cofacial metal–organic framework via single crystal electronic absorption spectroscopy

Gaining a fundamental understanding of charge transfer mechanisms in three-dimensional Metal–Organic Frameworks (MOFs) is crucial to the development of electroactive and conductive porous materials. These materials have potential in applications in porous conductors, electrocatalysts and energy storage devices; however the structure–property relationships pertaining to charge transfer and its quantification are relatively poorly understood. Here, the cofacial Cd(ii)-based MOF [Cd(BPPTzTz)(tdc)]·2DMF (where BPPTzTz = 2,5-bis(4-(pyridin-4-yl)phenyl)thiazolo[5,4-d]thiazole, tdc²⁻ = 2,5-thiophene dicarboxylate) exhibits Intervalence Charge Transfer (IVCT) within its three-dimensional structure by virtue of the close, cofacial stacking of its redox-active BPPTzTz ligands. The mixed-valence and IVCT properties are characterised using a combined electrochemical, spectroelectrochemical and computational approach. Single crystal electronic absorption spectroscopy was employed to obtain the solid-state extinction coefficient, enabling the application of Marcus–Hush theory. The electronic coupling constant, H_ab, of 145 cm⁻¹ was consistent with the localised mixed-valence properties of both this framework and analogous systems that use alternative methods to obtain the H_ab parameter. This work demonstrates the first report of the successful characterisation of IVCT in a MOF material using single crystal electronic absorption spectroscopy and serves as an attractive alternative to more complex methods due to its simplicity and applicability.

Gaining a fundamental understanding of charge transfer mechanisms in three-dimensional Metal–Organic Frameworks (MOFs) is crucial to the development of electroactive and conductive porous materials.     

Oxidative control over the morphology of Cu3(HHTP)2, a 2D conductive metal–organic framework

The morphology of electrically conductive metal–organic frameworks strongly impacts their performance in applications such as energy storage and electrochemical sensing. However, identifying the appropriate conditions needed to achieve a specific nanocrystal size and shape can be a time-consuming, empirical process. Here we show how partial ligand oxidation dictates the morphology of Cu₃(HHTP)₂ (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene), a prototypical 2D conductive metal–organic framework. Using organic quinones as the chemical oxidant, we demonstrate that partial oxidation of the ligand prior to metal binding alters the nanocrystal aspect ratio by over 60-fold. Systematically varying the extent of initial ligand oxidation leads to distinct rod, block, and flake-like morphologies. These results represent an important advance in the rational control of Cu₃(HHTP)₂ morphology and motivate future studies into how ligand oxidation impacts the nucleation and growth of 2D conductive metal–organic frameworks.

The morphology of a copper-based 2D conductive metal–organic framework can be tuned via controlled ligand oxidation. Using quinone oxidants, we show how partial ligand oxidation prior to metal binding alters the nanocrystal aspect ratio by >60-fold.     

Towards multi-colour strategies for the detection of oligonucleotide hybridization using quantum dots as energy donors in fluorescence resonance energy transfer (FRET)

The potential for a simultaneous two-colour diagnostic scheme for nucleic acids operating on the basis of fluorescence resonance energy transfer (FRET) has been demonstrated. Upon ultraviolet excitation, two-colours of CdSe/ZnS quantum dots with conjugated oligonucleotide probes act as energy donors yielding FRET-sensitized acceptor emission upon hybridization with fluorophore (Cy3 and Alexa647) labeled target oligonucleotides. Energy transfer efficiencies, Förster distances, changes in quantum yield and lifetime, and signal-to-noise with respect to non-specific adsorption have been investigated. The dynamic range and limit-of-detection are tunable with the concentration of QD-DNA conjugate. The Cy3 and Alexa647 acceptor schemes can detect target from 4 to 100% or 10 to 100% of the QD-DNA conjugate concentration, respectively. Nanomolar limits of detection have been demonstrated in this paper, however, results indicate that picomolar detection limits can be achieved with standard instrumentation. The use of an intercalating dye (ethidium bromide) as an acceptor to alleviate non-specific adsorption is also described and increases signal-to-noise from S/N < 2 to S/N = 9-10. The ethidium bromide system had a dynamic range from 8 to 100% of the QD-DNA conjugate concentration and could detect target in a matrix containing an excess of non-complementary nucleic acid.     

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.     

DNA mismatch detection by resonance energy transfer between ruthenium(II) and osmium(II) tris(2,2'-bipyridyl) chromophores

Octahedral tris-chelate complexes [M(II)(bpy)(3)](2+) (M = Ru or Os, bpy = 2,2'-bipyridyl), covalently attached to the 3'- and 5'-phosphates of two oligonucleotides, are juxtaposed when hybridized contiguously to a fully complementary DNA target. Visible metal-to-ligand charge-transfer (MLCT) excitation of the [Ru(II)(bpy)(3)](2+) unit leads to resonance energy transfer to the MLCT state of the [Os(II)(bpy)(3)](2+) moiety, with the energy transfer efficiency depending on the degree of hybridization. The extent of attenuation of the intense red luminescence from the Ru(II) chromophore hence allows highly sensitive structural probing of the assembly and constitutes a novel approach to DNA sensing which is capable of detecting mutations.     

A bis(amine–carboxylate) copper(II) coordination compound forms a two‐dimensional metal–organic framework when crystallized from water and methanol

When {2,2′‐[(2‐methyl‐2‐nitropropane‐1,3‐diyl)diimino]diacetato}copper(II), [Cu(C₈H₁₃N₃O₆)], (I), was crystallized from a binary mixture of methanol and water, a monoclinic two‐dimensional water‐ and methanol‐solvated metal–organic framework (MOF) structure, distinctly different from the known orthorhombic one‐dimensional coordination polymer of (I), was isolated, namely catena‐poly[[copper(II)‐μ₃‐2,2′‐[(2‐methyl‐2‐nitropropane‐1,3‐diyl)diimino]diacetato] methanol 0.45‐solvate 0.55‐hydrate], {[Cu(C₈H₁₃N₃O₆)]·0.45CH₃OH·0.55H₂O}_n, (II). The monoclinic structure of (II) comprises centrosymmetric dimers stabilized by a dative covalent Cu₂O₂ core and intramolecular N—H...O hydrogen bonds. Each dimer is linked to four neighbouring dimers via symmetry‐related (opposing) pairs of bridging carboxylate O atoms to generate a `diamondoid' net or two‐dimensional coordination network. Tight voids of 166 ų are located between these two‐dimensional MOF sheets and contain a mixture of water and methanol with fractional occupancies of 0.55 and 0.45, respectively. The two‐dimensional MOF sheets have nanometre‐scale spacings (11.2 Å) in the crystal structure. Hydrogen‐bonding between the methanol/water hydroxy groups and a Cu‐bound bridging carboxylate O atom apparently negates thermal desolvation of the structure below 358 K in an uncrushed crystal of (II).     

A new luminescent anionic metal–organic framework based on heterometallic zinc(II)–barium(II) for selective detection of Fe3+ and Cu2+ ions in aqueous solution

Over the past two decades, the development of novel inorganic–organic hybrid porous crystalline materials or metal–organic frameworks (MOFs) using crystal engineering has provoked significant interest due to their potential applications as functional materials. In this context, luminescent MOFs as fluorescence sensors have recently received significant attention for the sensing of ionic species and small molecules. In this work, a new luminescent heterometallic zinc(II)–barium(II)‐based anionic metal–organic framework, namely poly[imidazolium [triaqua(μ₆‐benzene‐1,3,5‐tricarboxylato)bariumtrizinc] tetrahydrate], {(C₃H₄N₂)[BaZn₃(C₉H₃O₆)₃(H₂O)₃]·4H₂O}_n ( 1 ), was synthesized under hydrothermal conditions and characterized. Compound 1 presents a three‐dimensional framework with an unprecedented (3,5)‐connected topology of the point symbol (3.9²).(3³.4².5.9³.10), and exhibits `turn‐off' luminescence responses for the Cu²⁺ and Fe³⁺ ions in aqueous solution based on significantly different quenching mechanisms.     

Determination of mercury(II) ions in seafood samples after extraction and preconcentration by a novel functionalized magnetic metal–organic framework nanocomposite

This work describes a novel functionalized magnetic metal–organic framework nanocomposite [(Fe₃O₄‐2,5‐dimercapto‐1,3,4‐thiadiazole)/metal–organic framework] and its application in the preconcentration of Hg(II) ions. The parameters affecting the preconcentration procedure were optimized by a Box–Behnken design through response surface methodology. Three variables (uptake time, magnetic nanosorbent amount, and pH value) were selected as the main factors affecting the sorption step, while four variables (type, volume, and concentration of the eluent; and elution time) were selected as main factors in the optimization study of the elution step. Following the sorption and elution of analytes, the ions were quantified by cold vapor atomic absorption spectrometry. Under the optimum conditions, the limit of detection was 0.01 ng/mL and all the relative standard deviations were less than 10%. The obtained sorption capacity (in mg/g) of this new sorbent was 124. Ultimately, this nanocomposite was successfully applied to the rapid extraction of trace quantities of Hg(II) ions in seafood samples and satisfactory results were obtained.     

Basic isoreticular metal–organic framework (IRMOF‐3) porous nanomaterial as a suitable and green catalyst for selective unsymmetrical Hantzsch coupling reaction

A catalytic amount of the basic metal–organic framework (IRMOF‐3) with organic substrates was found to be an efficient, selective and waste‐free green approach for the unsymmetrical Hantzsch coupling reaction. The catalyst can be isolated from the reaction mixture and reused at least four times. Copyright © 2014 John Wiley & Sons, Ltd.     

Characterization and gas adsorption of a novel three‐dimensional metal–organic framework (MOF) generated from a new polydentate fluorene‐bridged ligand

A polydentate ligand bridged by a fluorene group, namely 9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene (L), has been prepared under solvothermal conditions in acetonitrile. Crystals of the three‐dimensional metal–organic framework (MOF) poly[[[μ₃‐9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene‐κ³N:N′:O]bis(methanol‐κO)(μ‐sulfato‐κ²O:O′)nickel(II)] methanol disolvate], {[Ni(SO₄)(C₂₇H₂₄N₂O₂)(CH₃OH)]·2CH₃OH}_n, (I), were obtained by the solvothermal reaction of L and NiSO₄ in methanol. The ligand L forms a two‐dimensional network in the crystallographic bc plane via two groups of O—H…N hydrogen bonds and neighbouring two‐dimensional planes are completely parallel and stack to form a three‐dimensional structure. In (I), the Ni^II ions are linked by sulfate ions through Ni—O bonds to form inorganic chains and these Ni‐containing chains are linked into a three‐dimensional framework via Ni—O and Ni—N bonds involving the polydentate ligand L. With one of the hydroxy groups of L coordinating to the Ni^II atom, the torsion angle of the hydroxyethyl group changes from that of the uncoordinated molecule. In addition, the adsorption properties of (I) with carbon dioxide were investigated.