Exceptional Anhydrous Proton Conduction in Covalent Organic Frameworks.

Covalent organic frameworks (COFs) offer an irreplaceable platform for mass transport, as they provide aligned one-dimensional channels as pathways. Especially, proton conduction is of great scientific interest and technological importance. However, unlike proton conduction under humidity, anhydrous proton conduction remains a challenge, as it requires robust materials and proceeds under harsh conditions. Here, we report exceptional anhydrous proton conduction in stable crystalline porous COFs by integrating neat phosphoric acid into the channels to form extended hydrogen-bonding networks. The phosphoric acid networks in the pores are stabilized by hierarchical multipoint and multichain hydrogen-bonding interactions with the 3D channel walls. We synthesized five hexagonal COFs that possess different pore sizes, which are gradually tuned from micropores to mesopores. Remarkably, mesoporous COFs with a high pore volume exhibit an exceptional anhydrous proton conductivity of 0.31 S cm-1, which marks the highest conductivity among all examples reported for COFs. We observed that the proton conductivity is dependent on the pore volume, pore size, and content of phosphoric acid. Increasing the pore volume improves the proton conductivity in an exponential fashion. Remarkably, changing the pore volume from 0.41 to 1.60 cm3 g-1 increases the proton conductivity by 1150-fold. Interestingly, as the pore size increases, the activation energy barrier of proton conduction decreases in linear mode. The mesopores enable fast proton hopping across the channels, while the micropores follow sluggish vehicle conduction. Experiments on tuning phosphoric acid loading contents revealed that a well-developed hydrogen-bonding phosphoric acid network in the pores is critical for proton conduction.

Light-Gating Crystalline Porous Covalent Organic Frameworks.

We report light gating in synthetic one-dimensional nanochannels of stable crystalline porous covalent organic frameworks. The frameworks consist of 2D hexagonal skeletons that are extended over the x-y plane and stacked along the z-direction to create dense yet aligned 1D mesoporous channels. The pores are designed to be photoadaptable by covalently integrating tetrafluoro-substituted azobenzene units onto edges, which protrude from walls and offer light-gating machinery confined in the channels. The implanted tetrafluoroazobenzene units are thermally stable yet highly sensitive to visible light to induce photoisomerization between the E and Z forms. Remarkably, photoisomerization induces drastic changes in intrapore polarity as well as pore shape and size, which exert profound effects on the molecular adsorption of a broad spectrum of compounds, ranging from inorganic iodine to organic dyes, drugs, and enzymes. Unexpectedly, the systems respond rapidly to visible lights to gate the molecular release of drugs and enzymes. Photoadaptable covalent organic frameworks with reversibly convertible pores offer a platform for constructing light-gating porous materials and tailorable delivery systems, remotely controlled by visible lights.

Accelerating Anhydrous Proton Transport in Covalent Organic Frameworks: Pore Chemistry and its Impacts.

Proton conduction is important in both fundamental research and technological development. Here we report designed synthesis of crystalline porous covalent organic frameworks as a new platform for high-rate anhydrous proton conduction. By developing nanochannels with different topologies as proton pathways and loading neat phosphoric acid to construct robust proton carrier networks in the pores, we found that pore topology is crucial for proton conduction. Its effect on increasing proton conductivity is in an exponential mode other than linear fashion, endowing the materials with exceptional proton conductivities exceeding 10-2 S cm-1 over a broad range of temperature and a low activation energy barrier down to 0.24 eV. Remarkably, the pore size controls conduction mechanism, where mesopores promote proton conduction via a fast-hopping mechanism, while micropores follow a sluggish vehicle process. Notably, decreasing phosphoric acid loading content drastically reduces proton conductivity and greatly increases activation energy barrier, emphasizing the pivotal role of well-developed proton carrier network in proton transport. These findings and insights unveil a new general and transformative guidance for designing porous framework materials and systems for high-rate ion conduction, energy storage, and energy conversion.

Crystalline, Porous Helicene Covalent Organic Frameworks.

Helicenes are a class of fascinating chiral helical molecules with rich chemistry developed continuously over the past 100 years. Their helical, conjugated, and twisted structures make them attractive for constructing molecular systems. However, studies over the past century are mainly focused on synthesizing helicenes with increased numbers of aromatic rings and complex heterostructures, while research on inorganic, organic, and polymeric helicene materials is still embryonic. Herein, we report the first examples of helicene covalent organic frameworks, i.e., [7]Helicene sp2 c-COF-1, by condensing [7]Helicene dialdehyde with trimethyl triazine via the C=C bond formation reaction under solvothermal conditions. The resultant [7]Helicene sp2 c-COF-1 exhibits prominent X-ray diffraction peaks and assumes a highly ordered 2D lattice structure originated from the twisted configuration of [7]Helicene unit. The C=C linked [7]Helicene sp2 c-COF-1 materials exhibited extended π conjugation and broadly tuned their absorption, emission, redox activity, photoconductivity, and light-emitting activity, demonstrating rich multifunctionalities and great potentials in developing various applications. This work opens a way to a new family of COFs as well as helicene materials, enabling the exploration of unprecedented π architectures and properties.

Covalent Organic Frameworks: Linkage Chemistry and Its Critical Role in The Evolution of π Electronic Structures and Functions.

Covalent organic frameworks (COFs) provide a molecular platform for designing a novel class of functional materials with well-defined structures. A crucial structural parameter is the linkage, which dictates how knot and linker units are connected to form two-dimensional polymers and layer frameworks, shaping ordered π-array and porous architectures. However, the roles of linkage in the development of ordered π electronic structures and functions remain fundamental yet unresolved issues. Here we report the designed synthesis of COFs featuring four representative linkages: hydrazone, imine, azine, and C=C bonds, to elucidate their impacts on the evolution of π electronic structures and functions. Our observations revealed that the hydrazone linkage provides a non-conjugated connection, while imine and azine allow partial π conjugation, and the C=C bond permits full π-conjugation. Importantly, the linkage profoundly influences the control of π electronic structures and functions, unraveling its pivotal role in determining key electronic properties such as band gap, frontier energy levels, light absorption, luminescence, carrier density and mobility, and magnetic permeability. These findings highlight the significance of linkage chemistry in COFs and offer a general and transformative guidance for designing framework materials to achieve electronic functions.

Helicene Covalent Organic Frameworks for Robust Light Harvesting and Efficient Energy Transfers.

Helicenes represent a class of fascinating π compounds with fused yet folded backbones. Despite their broad structural diversity, harnessing helicenes to develop well-defined materials is still a formidable challenge. Here we report the synthesis of crystalline porous helicene materials by exploring helicenes to synthesize covalent 2D lattices and layered π frameworks. Topology-directed polymerization of [6]helicenes and porphyrin creates 2D covalent networks with alternate helicene-porphyrin alignment along the x and y directions at a 1.5-nm interval and develops [6]helicene frameworks through reversed anti-AA stack along the z direction to form segregated [6]helicene and porphyrin columnar π arrays. Notably, this π configuration enables the frameworks to be highly red luminescent with benchmark quantum yields. The [6]helicene frameworks trigger effieicnt intra-framework singlet-to-singlet state energy transfer from [6]helicene to porphyrin and facilitate intermolecular triplet-to-triplet state energy transfer from frameworks to molecular oxygen to produce reactive oxygen species, harvesting a wide range of photons from ultraviolet to near-infrared regions for light emitting and photo-to-chemical conversion. This study introduces a new family of extended frameworks, laying the groundwork for exploring well-defined helicene materials with unprecedented structures and functions.

Photoresponsive Covalent Organic Frameworks: Visible-Light Controlled Conversion of Porous Structures and Its Impacts.

Covalent organic frameworks are a novel class of crystalline porous polymers that enable molecular design of extended polygonal skeletons to attain well-defined porous structures. However, construction of a framework that allows remote control of pores remains a challenge. Here we report a strategy that merges covalent, noncovalent, and photo chemistries to design photoresponsive frameworks with reversibly and remotely controllable pores. We developed a topology-guided multicomponent polycondensation system that integrates protruded tetrafluoroazobenzene units as photoresponsive sites on pore walls at predesigned densities, so that a series of crystalline porous frameworks with the same backbone can be constructed to develop a broad spectrum of pores ranging from mesopores to micropores. Distinct from conventional azobenzene-based systems, the tetrafluoroazobenzene frameworks are highly sensitive to visible lights to undergo high-rate isomerization. The photoisomerization exerts profound effects on pore size, shape, number, and environment, as well as molecular uptake and release, rendering the system able to convert and switch pores reversibly and remotely with visible lights. Our results open a way to a novel class of smart porous materials with pore structures and functions that are convertible and manageable with visible lights.

Covalent Organic Frameworks: Reversible 3D Coalesce via Interlocked Skeleton-Pore Actions and Impacts on π Electronic Structures.

Covalent organic frameworks (COFs) create extended two-dimensional (2D) skeletons and aligned one-dimensional (1D) channels, constituting a class of novel π architectures with predesignable structural ordering. A distinct feature is that stacks of π building units in skeletons shape the pore walls, onto which a diversity of different units can be assembled to form various pore interfaces, opening a great potential to trigger a strong structural correlation between the skeleton and the pore. However, such a possibility has not yet been explored. Herein, we report reversible three-dimensional (3D) coalescence and interlocked actions between the skeleton and pore in COFs by controlling hydrogen-bonding networks in the pores. Introducing carboxylic acid units to the pore walls develops COFs that can confine water molecular networks, which are locked by the surface carboxylic acid units on the pore walls via multipoint, multichain, and multidirectional hydrogen-bonding interactions. As a result, the skeleton undergoes an interlocked action with pores to shrink over the x-y plane and to stack closer along the z direction upon water uptake. Remarkably, this interlocked action between the skeleton and pore is reversibly driven by water adsorption and desorption and triggers profound effects on π electronic structures and functions, including band gap, light absorption, and emission.

Covalent Organic Frameworks: Design, Synthesis, and Functions.

Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with permanent porosity and highly ordered structures. Unlike other polymers, a significant feature of COFs is that they are structurally predesignable, synthetically controllable, and functionally manageable. In principle, the topological design diagram offers geometric guidance for the structural tiling of extended porous polygons, and the polycondensation reactions provide synthetic ways to construct the predesigned primary and high-order structures. Progress over the past decade in the chemistry of these two aspects undoubtedly established the base of the COF field. By virtue of the availability of organic units and the diversity of topologies and linkages, COFs have emerged as a new field of organic materials that offer a powerful molecular platform for complex structural design and tailor-made functional development. Here we target a comprehensive review of the COF field, provide a historic overview of the chemistry of the COF field, survey the advances in the topology design and synthetic reactions, illustrate the structural features and diversities, scrutinize the development and potential of various functions through elucidating structure-function correlations based on interactions with photons, electrons, holes, spins, ions, and molecules, discuss the key fundamental and challenging issues that need to be addressed, and predict the future directions from chemistry, physics, and materials perspectives.

Haemolymph metabolomic differences in silkworms (Bombyx mori L.) under mulberry leaf and two artificial diet rearing methods.

The new technology of silkworm (Bombyx mori L.) artificial feed breeding has many characteristics and advantages. This study assessed silkworm rearing with mulberry leaf at all instars (MF) as the control, and used metabolomics to explore the differences in haemolymph metabolism of fifth instar silkworms under two modes of rearing with an artificial diet at all instars (AF) and rearing with an artificial diet during first to third instars and mulberry leaf during the fourth and fifth instars (AMF). The results show that, compared with silkworms of the MF group, the amount and fold change of various metabolites were higher in the haemolymph of AF group silkworms, and the metabolism of amino acids and uric acid, carbohydrates, lipids, and vitamins were changed. These changes may be the reasons for the poor performance of the AF silkworms. However, the amount and fold change of the various metabolites of silkworms in the AMF group were lower, and some metabolic pathways were more active. The amount of material and energy supply were greater. These changes could explain the high efficiency growth of body weight of silkworms after the conversion from artificial diet rearing to mulberry leaf rearing. These findings provide an important theoretical basis for the optimisation of artificial diet rearing technology for silkworms.

Hydroxide Anion Transport in Covalent Organic Frameworks.

Hydroxide anion transport is essential for alkaline fuel cells, but hydroxide anion has an inherently low conductivity owing to its small diffusion coefficient and high mass. Ordered open channels found in covalent organic frameworks are promising as pathways to enable hydroxide anion transport, but this remains to be explored. Here we report designed synthesis of anionic covalent organic frameworks that promote hydroxide anion transport across the one-dimensional channels. Engineering cationic chains with imidazolium termini onto the pore walls self-assembles a supramolecular interface of single-file hydroxide anion chains in the channels. The frameworks facilitate hydroxide anion transport to achieve an exceptional conductivity of 1.53 × 10-2 S cm-1 at 80 °C, which is 2-6 orders of magnitude higher than those of linear polymers and other porous frameworks. Impedance spectroscopy at different temperatures and studies on deuterated samples reveal that hydroxide anions transport via a proton-exchange hopping mechanism. These results open a way to design framework materials for energy conversions via engineering an anionic interface.

Efficacy and safety of mycophenolate mofetil in the treatment for IgA nephropathy: a meta-analysis of randomized controlled trials.

AIM: IgA nephropathy is virtually known as the most common glomerulopathy to end-stage renal failure in the world. Mycophenolate mofetil is a selective immunosuppressant widely used in organ transplantation, yet its tolerance and effectiveness in IgAN is controversial. METHODS: This is a systematic review and random-effects meta-analysis, searching PubMed, Embase, Te Cochrane Library, Science Citation Index, Ovid evidence-based medicine, Chinese Biomedical Literature and Chinese Science and Technology Periodicals. Screen out randomized controlled trials on patients with biopsy-proven IgA nephropathy and analysis mycophenolate mofetil treatment regimens used for therapy of IgA nephropathy. Complete remission and partial remission, doubling of creatinine level, proteinuria, incidence of end-stage kidney disease, infection, Cushing syndrome, diabetes, hepatic dysfunction or gastrointestinal symptoms, neurologic or visual ambiguity, acne, and alopecia were observed. RESULTS: Nine relevant trials were conducted with 587 patients enrolled. In Mycophenolate mofetil or plus medium/low-dose steroid comparing full-dose steroid alone or placebo, there was no significant difference. The risk of Cushing syndrome and diabetes had been significantly lowered with Mycophenolate mofetil-treated patients, while the risk of infection had been increased. CONCLUSIONS: Mycophenolate mofetil therapy did not differ in reducing proteinuria and Scr in patients with IgAN who had persistent proteinuria, while having fewer Cushing syndrome and diabetes risk and more infection risk. However, larger randomized studies are needed to reveal these results.

Ultrafast and Stable Proton Conduction in Polybenzimidazole Covalent Organic Frameworks via Confinement and Activation.

Polybenzimidazoles are engineering plastics with superb thermal stability and this specificity has sparked a wide-ranging research to explore proton-conducting materials. Nevertheless, such materials encounter challenging issues owing to phosphoric acid proton carrier leakage and slow proton transport. We report a strategy for designing porous polybenzimidazole frameworks to address these key fundamental issues. The built-in channels are designed to be one-dimensionally extended, unidirectionally aligned, and fully occupied by neat phosphoric acid, while the benzimidazole walls trigger multipoint, multichain, and multitype interactions to spatially confine a phosphoric acid network in pores and facilitate proton conduction via deprotonation. The materials exhibit ultrafast and stable proton conduction for low proton carrier content and activation energy-a set of features highly desired for proton transport. Our results offer a design strategy for the fabrication of porous polybenzimidazoles for use in energy conversion applications.

Designing Covalent Organic Frameworks with a Tailored Ionic Interface for Ion Transport across One-Dimensional Channels.

A strategy based on covalent organic frameworks for ultrafast ion transport involves designing an ionic interface to mediate ion motion. Electrolyte chains were integrated onto the walls of one-dimensional channels to construct ionic frameworks via pore surface engineering, so that the ionic interface can be systematically tuned at the desired composition and density. This strategy enables a quantitative correlation between interface and ion transport and unveils a full picture of managing ionic interface to achieve high-rate ion transport. Moreover, the effect of interfaces was scaled on ion transport; ion mobility is increased in an exponential mode with the ionic interface. This strategy not only sets a benchmark system but also offers a general guidance for designing ionic interface that is key to systems for energy conversion and storage.

Covalent Organic Frameworks: Chemical Approaches to Designer Structures and Built-In Functions.

A new approach has been developed to design organic polymers using topology diagrams. This strategy enables covalent integration of organic units into ordered topologies and creates a new polymer form, that is, covalent organic frameworks. This is a breakthrough in chemistry because it sets a molecular platform for synthesizing polymers with predesignable primary and high-order structures, which has been a central aim for over a century but unattainable with traditional design principles. This new field has its own features that are distinct from conventional polymers. This Review summarizes the fundamentals as well as major progress by focusing on the chemistry used to design structures, including the principles, synthetic strategies, and control methods. We scrutinize built-in functions that are specific to the structures by revealing various interplays and mechanisms involved in the expression of function. We propose major fundamental issues to be addressed in chemistry as well as future directions from physics, materials, and application perspectives.

Integrative Assessment of Mixture Toxicity of Three Ionic Liquids on Acetylcholinesterase Using a Progressive Approach from 1D Point, 2D Curve, to 3D Surface.

The joint toxicities of [BMIM]BF4, [BMIM]PF6, and [HMIM]BF4 on acetylcholinesterase (AChE) were systematically investigated by using a progressive approach from 1D single effect point, 2D concentration-response curve (CRC), to 3D equivalent-surface (ES) level. The equipartition equivalent-surface design (EESD) method was used to design 10 ternary mixtures, and the direct equipartition ray (EquRay) design was used to design 15 binary mixtures. The toxicities of ionic liquids (ILs) and their mixtures were determined using the microplate toxicity analysis (MTA) method. The concentration addition (CA), independent action (IA), and co-toxicity coefficient (CTC) were used as the additive reference model to analyze the toxic interaction of these mixtures. The results showed that the Weibull function fitted well the CRCs of the three ILs and their mixtures with the coefficient of determination (R2) greater than 0.99 and root-mean-square error (RMSE) less than 0.04. According to the CTC integrated with confidence interval (CI) method (CTCICI) developed in this study, the 25 mixtures were almost all additive action at 20% and 80% effect point levels. At 50% effect, at least half of the 25 mixtures were slightly synergistic action, and the remaining mixtures were additive action. Furthermore, the ESs and CRCs predicted by CA and IA were all within the CIs of mixture observed ESs and CRCs, respectively. Therefore, the toxic interactions of these 25 mixtures were actually additive action. The joint toxicity of the three ILs can be effectively evaluated by the ES method. We also studied the relationship between the mixture toxicities and component concentration proportions. This study can provide reference data for IL risk assessment of combined pollution.

Ion Conduction in Polyelectrolyte Covalent Organic Frameworks.

Covalent organic frameworks (COFs) with ordered one-dimensional channels could offer a predesigned pathway for ion motion. However, implanting salts into bare channels of COFs gives rise to a limited ion conductivity. Here, we report the first example of polyelectrolyte COFs by integrating flexible oligo(ethylene oxide) chains onto the pore walls. Upon complexation with lithium ions, the oligo(ethylene oxide) chains form a polyelectrolyte interface in the nanochannels and offer a pathway for lithium ion transport. As a result, the ion conductivity was enhanced by more than 3 orders of magnitude compared to that of ions across the bare nanochannels. The polyelectrolyte COFs promoted ion motion via a vehicle mechanism and exhibited enhanced cycle and thermal stabilities. These results suggest that the strategy for engineering a polyelectrolyte interface in the 1D nanochannels of COFs could open a new way to solid-state ion conductors.

Light-Emitting Covalent Organic Frameworks: Fluorescence Improving via Pinpoint Surgery and Selective Switch-On Sensing of Anions.

Covalent organic frameworks (COFs) offer ordered π structures that are useful for developing light-emitting materials. However, most COFs are weak in luminescence. Here we report the conversion of less emissive COFs into light-emitting materials via a pinpoint surgery on the pore walls. Deprotonation of the N-H bond to form an anionic nitrogen species in the hydrazone linkage can eliminate the nitrogen-related fluorescence quenching pathway. The resulting COF enhances the fluorescence in a linear proportion to the progress of deprotonation, achieving a 3.8-fold improved emission. This pinpoint N-H cleavage on the pore walls can be driven only by the fluoride anion while other halogen anions, including chloride, bromide, and iodide, remain inactive, enabling the selective fluorescence switch-on sensing of the fluoride anion at a ppb level.

Proton conduction in crystalline and porous covalent organic frameworks.

Progress over the past decades in proton-conducting materials has generated a variety of polyelectrolytes and microporous polymers. However, most studies are still based on a preconception that large pores eventually cause simply flow of proton carriers rather than efficient conduction of proton ions, which precludes the exploration of large-pore polymers for proton transport. Here, we demonstrate proton conduction across mesoporous channels in a crystalline covalent organic framework. The frameworks are designed to constitute hexagonally aligned, dense, mesoporous channels that allow for loading of N-heterocyclic proton carriers. The frameworks achieve proton conductivities that are 2-4 orders of magnitude higher than those of microporous and non-porous polymers. Temperature-dependent and isotopic experiments revealed that the proton transport in these channels is controlled by a low-energy-barrier hopping mechanism. Our results reveal a platform based on porous covalent organic frameworks for proton conduction.

EFFICACY AND SAFETY OF INTRAVITREAL CONBERCEPT INJECTIONS IN MACULAR EDEMA SECONDARY TO RETINAL VEIN OCCLUSION.

PURPOSE: To assess the efficacy and safety of intravitreal conbercept injections in patients with macular edema secondary to retinal vein occlusion (RVO). METHODS: A prospective, Phase II clinical trial was performed on 60 patients with macular edema secondary to RVO. Thirty patients had branch RVO (BRVO) and 30 had central RVO (CRVO). Each patient received intravitreal injections of conbercept monthly up to 3 months, followed by monthly evaluation and injection pro re nata to Month 9. RESULTS: The average change of best-corrected visual acuity from baseline to Month 9 was 17.83 ± 10.89 letters in BRVO and 14.23 ± 11.74 letters in CRVO. The change in best-corrected visual acuity was not statistically different between the groups (P = 0.216). The mean reduction of central retina thickness from baseline to Month 9 was 289.97 ± 165.42 µm and 420.47 ± 235.89 µm in BRVO and CRVO, respectively. The mean numbers of injections was 7.14 ± 1.90 in BRVO and 7.59 ± 1.39 in CRVO from baseline to Month 9 (P = 0.4705). There were 7 serious adverse events (SAEs) in 5 patients (8.33%, 2 BRVO and 3 CRVO). All the SAEs were nonocular and were not related to the drug or the injection procedure. CONCLUSION: Intravitreal injections of conbercept demonstrated a generally favorable safety and tolerability profile as well as efficacy in the treatment of macular edema due to RVO.