Hydrogen-bonded Organic Framework Research Articles

A Hydrogen-Bonded Organic Framework-Based Mitochondrion-Targeting Bioorthogonal Platform for the Modulation of Mitochondrial Epigenetics.

Bioorthogonal chemistry represents a powerful tool in chemical biology, which shows great potential in epigenetic modulation. As a proof of concept, the epigenetic modulation model of mitochondrial DNA (mtDNA) is selected because mtDNA establishes a relative hypermethylation stage under oxidative stress, which impairs the mitochondrion-based therapeutic effect during cancer therapy. Herein, we design a new biocompatible hydrogen-bonded organic framework (HOF) for a HOF-based mitochondrion-targeting bioorthogonal platform TPP@P@PHOF-2. PHOF-2 can activate a prodrug (pro-procainamide) in situ, which can specifically inhibit DNA methyltransferase 1 (DNMT1) activity and remodel the epigenetic modification of mtDNA, making it more susceptible to ROS damage. In addition, PHOF-2 can also catalyze artemisinin to produce large amounts of ROS, effectively damaging mtDNA and achieving better chemodynamic therapy demonstrated by both in vitro and in vivo studies. This work provides new insights into developing advanced bioorthogonal therapy and expands the applications of HOF and bioorthogonal catalysis.

Metal Hydrogen-Bonded Organic Frameworks as Open Lewis Acid Catalysts for Two Types of CO2 Transformations.

Efficient and multiple CO2 utilization into high-value-added chemicals holds significant importance in carbon neutrality and industry production. However, most catalysis systems generally exhibit only one type of CO2 transformation with the efficiency to be improved. The restricted abundance of active catalytic sites or an inefficient utilization rate of these sites results in the constraint. Consequently, we designed and constructed two metal hydrogen-bonded organic frameworks (M-HOFs) {[M3(L3-)2(H2O)10]·2H2O}n (M = Co (1), Ni (2); L = 1-(4-carboxyphenyl)-1H-pyrazole-3,5-dicarboxylic acid) in this research. 1 and 2 are well-characterized, and both show excellent stability. The networks connected by multiple hydrogen bonds enhance the structural flexibility and create accessible Lewis acidic sites, promoting interactions between the substrates and catalytic centers. This enhancement facilitates efficient catalysis for two types of CO2 transformations, encompassing both cycloaddition reactions with epoxides and aziridines to afford cyclic carbonates and oxazolidinones. The catalytic activities (TON/TOF) are superior compared with those of most other catalysts. These heterogeneous catalysts still exhibited high performance after being reused several times. Mechanistic studies indicated intense interactions between the metal sites and substrates, demonstrating the reason for efficient catalysis. This marks the first instance on M-HOFs efficiently catalyzing two types of CO2 conversions, finding important significance for catalyst design and CO2 utilization.

Luminescent lanthanide hydrogen-bonded organic frameworks for rapid detection of benzophenone-3

2-hydroxy-4-methoxybenzophenone (BP-3) is a common ingredient in sunscreens that can protect human hair and skin from ultraviolet rays. However, it is poisonous to a number of marine organisms, such as algae and corals. Herein, we constructed a new hydrogen-bonded organic framework (HOF) by assembling melamine with pyridine 2,6-dicarboxylic acid (MA-DPA). Subsequently, lanthanide HOF (Ln@MA-DPA) was obtained by anchoring lanthanide ions to the HOF via the coordination of surface carboxylic acid and nitrogen atom. Significantly, Tb@MA-DPA exhibits exceptional luminescent sensing behavior towards BP-3 in aqueous condition, with a limit of detection (LOD) as low as 0.72 μM, and possesses the advantages of high selectivity, fast response and recyclability. We believe that the reported sensor will undoubtedly expand the application scope of HOFs and offers a novel avenue for utilizing HOFs in marine pollution monitoring.

Hypoxia-Responsive Hydrogen-Bonded Organic Framework-Mediated Protein Delivery for Cancer Therapy.

The efficient delivery of therapeutic proteins to tumor sites is a promising cancer treatment modality. Hydrogen-bonded organic frameworks (HOFs) are successfully used for the protective encapsulation of proteins; however, easy precipitation and lack of controlled release of existing HOFs limit their further application for protein delivery in vivo. Here, a hypoxia-responsive HOF, self-assembled from azobenzenedicarboxylate/polyethylene glycol-conjugated azobenzenedicarboxylate and tetrakis(4-amidiniumphenyl)methane through charge-assisted hydrogen-bonding, is developed for systemic protein delivery to tumor cells. The newly generated HOF platform efficiently encapsulates representative cytochrome C, demonstrating good dispersibility under physiological conditions. Moreover, it can respond to overexpressed reductases in the cytoplasm under hypoxic conditions, inducing fast intracellular protein release to exert therapeutic effects. The strategy presented herein can be applied to other therapeutic proteins and can be expanded to encompass more intrinsic tumor microenvironment stimuli. This offers a novel avenue for utilizing HOFs in protein-based cancer therapy.

Reticular syntheses of hydrogen-bonded organic frameworks based on pyrazole tetramers with tunable electrostatic potential for enhanced C2H2/CO2 separation

Reticular chemistry has been widely used to predict and design structures of MOFs and COFs, but it still limited in HOFs due to the flexible and fragile nature of hydrogen bonding. Herein, by employing the N-H···N hydrogen-bonding tetramers to connect the pyrazole monomers, we realize the reticular syntheses of three isostructural HOFs (HOF-FJU-45, HOF-FJU-46 and HOF-FJU-47) with tunable pore environments and explore their separation performance toward C2H2/CO2 mixtures. Among these three HOFs, the electrostatic potential of pore surface in HOF-FJU-47a with tetraphenyladamantane core is complementary to C2H2, enabling it to perform better C2H2/CO2 separation performance than HOF-FJU-45a with tetraphenylmethane core and HOF-FJU-46a with tetraphenylsilane core. Dynamic breakthrough experiments also confirm that HOF-FJU-47a can achieve superior C2H2/CO2 separation performance with a balanced C2H2 working capacity (1.98 mmol g−1) and separation factor (5.5) in HOFs materials. The multiple host–guest interactions between C2H2 and the framework of HOF-FJU-47a are further revealed by theoretical calculations.

Mechano-responsive and acid stimuli-responsive luminescence of a hydrogen-bonded organic frameworks

Stimuli-responsive materials are capable of changing their chemical or physical properties when exposed to external stimuli, showing a wide range of potential applications such as drug delivery, sensing, smart coatings, and artificial muscles. Here, a micron-sized hydrogen-bonded organic framework PFC-1 was constructed and its mechanical and acid stimuli-responsive luminescence were investigated. It was found that the fluorescence of PFC-1 aqueous suspension is affected HCl concentrations. The pristine PFC-1 aqueous suspension exhibits an emission peak with high fluorescence intensity at 440 nm and two weak emission shoulders at 475 nm and 535 nm, respectively. Upon the addition of hydrochloric acid, there is a gradual reduction in the peak intensities at 440 nm and 475 nm, while the peak intensity at 535 nm remains relatively unchanged, resulting in a progressive shift in fluorescence color from blue to green. Mechanical grinding induces approximate 30 nm blue-shift in the fluorescence emission peak, a change that is reversible upon immersing the powder in ethanol for 60 min. This work contributes to the development of stimuli-responsive hydrogen-bonded organic framework materials with potential applications in acid and pressure fluorescence sensing.

Supramolecular Entanglement in a Hydrogen-Bonded Organic Framework Enables Flexible-Robust Porosity for Highly Efficient Purification of Natural Gas.

The development of porous materials with flexible-robust characteristics shows some unique advantages to target high performance for gas separation, but remains a daunting challenge to achieve so far. Herein, we report a carboxyl-based hydrogen-bonded organic framework (ZJU-HOF-8a) with flexible-robust porosity for efficient purification of natural gas. ZJU-HOF-8a features a four-fold interpenetrated structure with dia topology, wherein abundant supramolecular entanglements are formed between the adjacent subnetworks through weak intermolecular hydrogen bonds. This structural configuration could not only stabilize the whole framework to establish the permanent porosity, but also enable the framework to show some flexibility due to its weak intermolecular interactions (so-called flexible-robust framework). The flexible-robust porosity of ZJU-HOF-8a was exclusively confirmed by gas sorption isotherms and single-crystal X-ray diffraction studies, showing that the flexible pore pockets can be opened by C3H8 and n-C4H10 molecules rather by C2H6 and CH4. This leads to notably higher C3H8 and n-C4H10 uptakes with enhanced selectivities than C2H6 over CH4 under ambient conditions, affording one of the highest n-C4H10/CH4 selectivities. The gas-loaded single-crystal structures coupled with theoretical simulations reveal that the loading of n-C4H10 can induce an obvious framework expansion along with pore pocket opening to improve n-C4H10 uptake and selectivity, while not for C2H6 adsorption. This work suggests an effective strategy of designing flexible-robust HOFs for improving gas separation properties.

A mitochondria-targeted biocompatible photothermal nanoscale hydrogen-bonded organic framework for effective multimodal-imaging guided breast cancer therapy

Organic small-molecule photothermal agents (smPTAs) have been extensively studied for biomedical applications due to their good biocompatibility comparing with inorganic materials. However, most smPTAs suffer from water insolubility, even organic solvents insolubility, poor bio- and photo-stability, and short blood half-life. Herein, a new type of salinized 4,4′-(benzo[1,2-d:4,5-d']bis(thiazole)-2,6-diyl)dibenzoic acid (BBTDB-Na) smPTA is synthesized via a cyano group of 2-cyano-benzothiazole (CBT)-1,2-aminothiol group of cysteine (Cys) click condensation reaction, and photothermal nanoscale hydrogen-bonded organic frameworks (BT-nHOFs) is further constructed through a facile self-assembly strategy. The prepared BT-nHOFs exhibit a fusiform shape and bisthiazole structure, resulting in good cellular uptake and mitochondrial targeting effects. The well-organized structure of HOFs enables excellent photostability and high photothermal efficiency (51.4 %). Under 808 nm laser irradiation, the BT-nHOFs show favorable photothermal effects on breast cancer cells in vitro and in vivo, indicating that BT-nHOFs can act as a biocompatible PTA candidate for clinical applications. Besides, the fluorescence features, photoacoustic ability, cargo loading capacity of BT-nHOFs furnish multimodal imaging-guided precise photothermal therapy. In summary, this work paves a new way for the development of photothermal HOFs by salinizing insoluble smPTA and demonstrates their great potential for clinical application in phototheranostics.

Stable hydrogen-bonded organic frameworks and their photo- and electro-responses

Stable hydrogen-bonded organic frameworks and their photo- and electro-responses

Vitrification-enabled enhancement of proton conductivity in hydrogen-bonded organic frameworks

Hydrogen-bonded organic frameworks (HOFs) are versatile materials with potential applications in proton conduction. Traditional approaches involve incorporating humidity control to address grain boundary challenges for proton conduction. This study finds vitrification as an alternative strategy to eliminate grain boundary effect in HOFs by rapidly melt quenching the kinetically stable HOF-SXU-8 to glassy state HOF-g. Notably, a remarkable enhancement in proton conductivity without humidity was achieved after vitrification, from 1.31 × 10−7 S cm−1 to 5.62× 10−2 S cm−1 at 100 °C. Long term stability test showed negligible performance degradation, and even at 30 °C, the proton conductivity remained at high level of 1.2 × 10−2 S cm−1. Molecule dynamics (MD) simulations and X-ray total scattering experiments reveal the HOF-g system is consisted of three kinds of clusters, i.e., 1,5-Naphthalenedisulfonic acid (1,5-NSA) anion clusters, N,N-dimethylformamide (DMF) molecule clusters, and H+-H2O clusters. In which, the H+ plays an important role to bridge these clusters and the high conductivity is mainly related to the H+ on H3O+. These findings provide valuable insights for optimizing HOFs, enabling efficient proton conduction, and advancing energy conversion and storage devices.

Iron modified hydrogen-bonded organic framework as fluorescent sensor for ascorbic acid detection

Herein, iron modified hydrogen-bonded organic framework (Fe-HOF) was successfully prepared by introducing the yellow-green fluorescent ligand 2,5-dihydroxyterephthalic acid into HOF and then modifying Fe3+. A simple turn-on fluorescence strategy is proposed for the detection of ascorbic acid (AA) based on Fe-HOF. Fe3+ could effectively quench fluorescence emission of HOF. In the presence of AA, Fe3+ was reduced to Fe2+, which led to the fluorescence recovery of HOF, thus realizing the fluorescence quantitative detection of AA. These fluorescence responsive behaviors of Fe-HOF ensure fluorescence assay of AA within 0.5 − 8 μM, along with a limit of detection (LOD) of 0.14 μM. The sensing platform could realize the rapid detection of ascorbic acid in vitamin C pills, tablets and beverages in the detection of ascorbic acid with good recoveries.

Enhancing catalytic activity through self-assembled hydrogen-bonded organic framework-based catalysts at liquid/liquid interface for 4-nitrophenol reduction and energy challenges in methanol fuel cell

Hydrogen-bonded organic frameworks (HOFs) are pure organic framework structures endowed with appropriate flexibility and porosity, which have attracted special attention in the field of energy and water, air, and soil remediation. In this study, six HOF-based materials were synthesized as thin film at the liquid/liquid (toluene/water) interface and characterized by FT-IR, Raman, UV–Vis, PXRD, ICP, AFM, SEM, TGA, and BET techniques. The self-assembled HOF-based thin films were employed as catalysts for the 4-nitrophenol removal from water medium and, for the first time, for methanol oxidation of fuel cell, with satisfying results. Simultaneous in situ catalyst formation and 4-nitrophenol reduction occurred in the case of Pt(0)@HOF thin film, but an extraordinary removal (not reduction) occurred in the presence of Pt(0)-trimesic acid thin film by formation of a new HOF from trimesic acid and 4-nitrophenol. Successful reduction of 4-nitrophenol occurred also in the presence of freshly prepared Pt(0)-trimesic acid, Pt(0)-melamine and Pt(0)@HOF catalysts (ex situ strategy). The chemical and thermal stability of HOF structure was improved by the interpenetration of ZIF-8 crystal structure, by increasing the hydrogen bonding and π-π stacking in the presence of 2-methylimidazole. The interpenetration of ZIF-8 to the crystal structure of HOF caused a significant decrease of the pore diameter of the structure. These pores acted as specific sites for the guest molecules, and their dimensions did not permit 4-nitrophenol to penetrate into the cavity of structures whereas allowed methanol penetration into these cavities due to its smaller size.

Hydrogen-bonded organic framework modified separator for simultaneously enhancing the safety and electrochemical performance of Ni-rich lithium-ion battery

Nickel-rich layered oxide cathode (LiNixCoyMn1−x−yO2, x > 0.5, NCM) shows substantial potential for applications in longer-range electrical vehicles. However, the rapid capacity decay and serious safety concerns impede its practical viability. This work provides a hydrogen-bonded organic framework (HOF) modification strategy to simultaneously improve the electrochemical performance, thermal stability and incombustibility of separator. Melamine cyanurate (MCA), as a low-cost and reliable flame-retardant HOF, was implemented in the separator modification layer, which can prevent the battery short circuit even at a high temperature. In addition, the supermolecule properties of MCA provide unique physical and chemical microenvironment for regulating ion-transport behavior in electrolyte. The MCA coating layer enabled the nickel-rich layered oxide cathode with a high-capacity retention of 90.3% after 300 cycles at 1.0 C. Collectively, the usage of MCA in lithium-ion batteries (LIBs) affords a simple, low-cost and efficient strategy to improve the security and service life of nickel-rich layered cathodes.

Ultrasensitive dual-mode detection of amyloid β oligomer via Au NRs modulated photoelectrochemical/electrochemiluminescent response from HOFs/g-C3N4

In this work, a heterojunction composite of HOFs/g-C3N4 was synthesized using solution-plasticized self-assembly of g-C3N4 nanosheet on hydrogen-bonded organic frameworks (HOFs). HOFs/g-C3N4 was then used as a substrate material to construct a novel photoelectrochemical/electrochemiluminescent (PEC/ECL) biosensor for the detection of amyloid β oligomer (Aβo). HOFs/g-C3N4 composites were first drop-coated on the electrode surface. Subsequently, the Aβ aptamer was modified on the electrode surface via amide bonding. The target Aβo and the gold nanorods (Au NRs)-labeled Aβ recognition peptide (Au NRs-KLVFF) were simultaneously dropped onto the electrode surface, thus a “sandwich” dual-mode biosensor was constructed. In the PEC detection of the Aβo, the surface plasmon resonance effect of Au NRs enhanced the visible absorption of HOF/g-C3N4, and the sensor exhibited a "signal-on" photocurrent signal. Meanwhile, the ECL emission spectrum of HOF/g-C3N4 in ECL mode overlaps with the ultraviolet-visible (UV) absorption of Au NRs, and the sensor signal showed a “signal-off” ECL response. Under the optimal conditions experiments, the constructed dual-mode biosensor showed a wide detection range and low detection limit for Aβo. The proposed dual-mode detection method has a detection range of 10 fM to 10 nM with a detection limit of 5.97 fM for PEC detection and a detection range of 0.1 pM to 1.0 μM with a detection limit of 0.051 pM for ECL detection respectively. Additionally, the detection method achieved satisfactory results in the analysis of real samples. Dual-mode sensing platform provides a new strategy for HOFs application in PEC/ECL assay and sensitive detection of AβO.

Construction of Adaptive Deformation Block: Rational Molecular Editing of the N-Rich Host Molecule to Remove Water from the Energetic Hydrogen-Bonded Organic Frameworks.

Energetic hydrogen-bonded organic frameworks (E-HOFs), as a type of energetic material, spark fresh vitality to the creation of high energy density materials (HEDMs). However, E-HOFs containing cations and anions face challenges such as reduced energy density due to the inclusion of crystal water. In this work, the modification of amino groups in N-rich organic units could form a smart building block of hydrogen-bonded frameworks capable of changing the volume of the void space in the molecule through adaptive deformation of E-MOF blocks, thus enabling the replacement of water. Based on the above strategy, we report an interesting example of a series of hydrogen-bonded organic frameworks (E-HOF 2a and 3a) synthesized using a facile method. The crystal structure data of all of the compounds were also obtained in this work. Anhydrous 2a and 3a exhibit higher density, good thermal stability, and low mechanical sensitivity. The strategy of covalent bond modification for the host molecules of energetic frameworks shows enormous potential in eliminating the crystalline H2O of hydration and exploring high energy density materials.

Structural Design and Energy and Environmental Applications of Hydrogen-Bonded Organic Frameworks: A Systematic Review.

Hydrogen-bonded organic frameworks (HOFs) are emerging porous materials that show high structural flexibility, mild synthetic conditions, good solution processability, easy healing and regeneration, and good recyclability. Although these properties give them many potential multifunctional applications, their frameworks are unstable due to the presence of only weak and reversible hydrogen bonds. In this work, the development history and synthesis methods of HOFs are reviewed, and categorize their structural design concepts and strategies to improve their stability. More importantly, due to the significant potential of the latest HOF-related research for addressing energy and environmental issues, this work discusses the latest advances in the methods of energy storage and conversion, energy substance generation and isolation, environmental detection and isolation, degradation and transformation, and biological applications. Furthermore, a discussion of the coupling orientation of HOF in the cross-cutting fields of energy and environment is presented for the first time. Finally, current challenges, opportunities, and strategies for the development of HOFs to advance their energy and environmental applications are discussed.

Protein‐Integrated Hydrogen‐Bonded Organic Frameworks: Chemistry and Biomedical Applications

AbstractHydrogen‐bonded organic frameworks (HOFs) are porous nanomaterials that offer exceptional biocompatibility and versatility for integrating proteins for biomedical applications. This minireview concisely discusses recent advancements in the chemistry and functionality of protein‐HOF interfaces. It particularly focuses on strategic methodologies, such as the careful selection of building blocks and the genetic engineering of proteins, to facilitate protein‐HOF interactions. We examine the role of enzyme encapsulation within HOFs, highlighting its capability to preserve enzyme function, a crucial aspect for applications in biosensing and disease diagnosis. Moreover, we discuss the emerging utility of nanoscale HOFs for intracellular protein delivery, illustrating their applicability as nanoreactors for intracellular catalysis and neuroprotective biorthogonal catalysis within cellular compartments. We highlight the significant advancement of designing biodegradable HOFs tailored for cytosolic protein delivery, underscoring their promising application in targeted cancer therapies. Finally, we provide a perspective viewpoint on the design of biocompatible protein‐HOF assemblies, underlining their promising prospects in drug delivery, disease diagnosis, and broader biomedical applications.

Protein-Integrated Hydrogen-Bonded Organic Frameworks: Chemistry and Biomedical Applications.

Hydrogen-bonded organic frameworks (HOFs) are porous nanomaterials that offer exceptional biocompatibility and versatility for integrating proteins for biomedical applications. This minireview concisely discusses recent advancements in the chemistry and functionality of protein-HOF interfaces. It particularly focuses on strategic methodologies, such as the careful selection of building blocks and the genetic engineering of proteins, to facilitate protein-HOF interactions. We examine the role of enzyme encapsulation within HOFs, highlighting its capability to preserve enzyme function, a crucial aspect for applications in biosensing and disease diagnosis. Moreover, we discuss the emerging utility of nanoscale HOFs for intracellular protein delivery, illustrating their applicability as nanoreactors for intracellular catalysis and neuroprotective biorthogonal catalysis within cellular compartments. We highlight the significant advancement of designing biodegradable HOFs tailored for cytosolic protein delivery, underscoring their promising application in targeted cancer therapies. Finally, we provide a perspective viewpoint on the design of biocompatible protein-HOF assemblies, underlining their promising prospects in drug delivery, disease diagnosis, and broader biomedical applications.

Hydrogen‐Bonded Organic Framework Supporting Atomic Bi−N2O2 Sites for High‐Efficiency Electrocatalytic CO2 Reduction

AbstractSingle atomic catalysts (SACs) offer a superior platform for studying the structure–activity relationships during electrocatalytic CO2 reduction reaction (CO2RR). Yet challenges still exist to obtain well‐defined and novel site configuration owing to the uncertainty of functional framework‐derived SACs through calcination. Herein, a novel Bi−N2O2 site supported on the (1 1 0) plane of hydrogen‐bonded organic framework (HOF) is reported directly for CO2RR. In flow cell, the target catalyst Bi1‐HOF maintains a faradaic efficiency (FE) HCOOH of over 90 % at a wide potential window of 1.4 V. The corresponding partial current density ranges from 113.3 to 747.0 mA cm−2. And, Bi1‐HOF exhibits a long‐term stability of over 30 h under a successive potential‐step test with a current density of 100–400 mA cm−2. Density function theory (DFT) calculations illustrate that the novel Bi−N2O2 site supported on the (1 1 0) plane of HOF effectively induces the oriented electron transfer from Bi center to CO2 molecule, reaching an enhanced CO2 activation and reduction. Besides, this study offers a versatile method to reach series of M−N2O2 sites with regulable metal centers via the same intercalation mechanism, broadening the platform for studying the structure–activity relationships during CO2RR.

Hydrogen-Bonded Organic Framework Supporting Atomic Bi-N2O2 Sites for High-Efficiency Electrocatalytic CO2 Reduction.

Single atomic catalysts (SACs) offer a superior platform for studying the structure-activity relationships during electrocatalytic CO2 reduction reaction (CO2RR). Yet challenges still exist to obtain well-defined and novel site configuration owing to the uncertainty of functional framework-derived SACs through calcination. Herein, a novel Bi-N2O2 site supported on the (1 1 0) plane of hydrogen-bonded organic framework (HOF) is reported directly for CO2RR. In flow cell, the target catalyst Bi1-HOF maintains a faradaic efficiency (FE) HCOOH of over 90 % at a wide potential window of 1.4 V. The corresponding partial current density ranges from 113.3 to 747.0 mA cm-2. And, Bi1-HOF exhibits a long-term stability of over 30 h under a successive potential-step test with a current density of 100-400 mA cm-2. Density function theory (DFT) calculations illustrate that the novel Bi-N2O2 site supported on the (1 1 0) plane of HOF effectively induces the oriented electron transfer from Bi center to CO2 molecule, reaching an enhanced CO2 activation and reduction. Besides, this study offers a versatile method to reach series of M-N2O2 sites with regulable metal centers via the same intercalation mechanism, broadening the platform for studying the structure-activity relationships during CO2RR.