Regulating Benzene Ring Number as Connector in Covalent Organic Framework for Boosting Photosynthesis of H2O2 from Seawater.

Photosynthesis of H2O2 from seawater represents a promising pathway to acquire H2O2, but it is still restricted by the lack of a highly active photocatalyst. In this work, we propose a convenient strategy of regulating the number of benzene rings to boost the catalytic activity of materials. This is demonstrated by ECUT-COF-31 with adding two benzene rings as the connector, which can result in 1.7-fold enhancement in the H2O2 production rate relative to ECUT-COF-30 with just one benzene ring as the connector. The reason for enhancement is mainly due to the release of *OOH from the surface of catalyst and the final formation of H2O2 being easier in ECUT-COF-31 than in ECUT-COF-30. Moreover, ECUT-COF-31 provides a stable photogeneration of H2O2 for 70 h, and a theoretically remarkable H2O2 production of 58.7 mmol per day from seawater using one gram of photocatalyst, while the cost of the used raw material is as low as 0.24 $/g.

High-Strength Polycrystalline Covalent Organic Framework with Abnormal Thermal Transport Insensitive to Grain Boundary.

Grain boundaries (GBs) in two-dimensional (2D) covalent organic frameworks (COFs) unavoidably form during the fabrication process, playing pivotal roles in the physical characteristics of COFs. Herein, molecular dynamics simulations were employed to elucidate the fracture failure and thermal transport mechanisms of polycrystalline COFs (p-COFs). The results revealed that the tilt angle of GBs significantly influences out-of-plane wrinkles and residual stress in monolayer p-COFs. The tensile strength of p-COFs can be enhanced and weakened with the tilt angle, which exhibits an inverse relationship with the defect density. The crack always originates from weaker heptagon rings during uniaxial tension. Notably, the thermal transport in p-COFs is insensitive to the GBs due to the variation of minor polymer chain length at defects, which is abnormal for other 2D crystalline materials. This study contributes insights into the impact of GBs in p-COFs and offers theoretical guidance for structural design and practical applications of advanced COFs.

Modulating Narrow Bandgap in a Diacetylene Functionalized Woven Covalent Organic Framework as a Visible Light Responsive Photocatalyst.

Woven covalent organic frameworks (COF) possess three dimensional frameworks with spatially isolated Cu(I) centers and have promising optoelectronic properties because of metal to ligand charge transfer (MLCT). However, despite their potential, woven COFs have not yet been investigated as photocatalysts. In this study, we developed a new woven COF, Cu-PhenBDA-COF, functionalized with diacetylene bonds. Cu-PhenBDA-COF was fully characterized, and the optoelectronic and photocatalytic properties were compared to previously reported Cu-COF-505. The diacetylene bonds of the linker positively impacted the optoelectronic properties of Cu-PhenBDA-COF and resulted in a narrower band gap and better charge separation efficiency. When the Cu(I) center was removed from both woven COFs, the absorption edge was blue shifted, resulting in a wider band gap, and there was a considerable decrease in the charge separation efficiency, underscoring the pivotal role of MLCT. This trend was reflected in the photocatalytic activity of the woven COFs toward the degradation of sulfamethoxazole in water, where the highest reaction rate constant (k app ) was recorded for the metallated diacetylene functionalized woven COF, Cu-PhenBDA-COF.

Propelling Multi-Modal Therapeutics of PEEK Implants through the Power of NO evolving Covalent Organic Frameworks (COFs).

The design and fabrication of NO-evolving core-shell nanoparticles (denoted as NC@Fe), comprised of BNN6-laden COF@Fe3 O4 nanoparticles, are reported. This innovation extends to the modification of 3D printed polyetheretherketone scaffolds with NC@Fe, establishing a pioneering approach to multi-modal bone therapy tailored to address complications such as device-associated infections and osteomyelitis. This work stands out prominently from previous research, particularly those relying on the use of antibiotics, by introducing a bone implant capable of simultaneous NO gas therapy and photothermal therapy (PPT). Under NIR laser irradiation, the Fe3 O4 NP core (photothermal conversion agent) within NC@Fe absorbs photoenergy and initiates electron transfer to the loaded NO donor (BNN6), resulting in controlled NO release. The additional heat generated through photothermal conversion further propels the NC@Fe nanoparticles, amplifying the therapeutic reach. The combined effect of NO release and PPT enhances the efficacy in eradicating bacteria over a more extensive area around the implant, presenting a distinctive solution to conventional challenges. Thorough in vitro and in vivo investigations validate the robust potential of the scaffold in infection control, osteogenesis, and angiogenesis, emphasizing the timeliness of this unique solution in managing complicated bone related infectious diseases.

An Appraisal for Providing Charge Transfer (CT) Through Synthetic Porous Frameworks for their Semiconductor Applications.

In recent years, there has been considerable focus on the development of charge transfer (CT) complex formation as a means to modify the band gaps of organic materials. In particular, CT complexes alternate layers of aromatic molecules with donor (D) and acceptor (A) properties to provide inherent electrical conductivity. In particular, the synthetic porous frameworks as attractive D-A components have been extensively studied in recent years in comparison to existing D-A materials. Therefore, in this work, the synthetic porous frameworks are classified into conjugated microporous polymers (CMPs), covalent organic frameworks (COFs), and metal-organic frameworks (MOFs) and compare high-quality materials for CT in semiconductors. This work updates the overview of the above porous frameworks for CT, starting with their early history regarding their semiconductor applications, and lists CT concepts and selected key developments in their CT complexes and CT composites. In addition, the network formation methods and their functionalization are discussed to provide access to a variety of potential applications. Furthermore, several theoretical investigations, efficiency improvement techniques, and a discussion of the electrical conductivity of the porous frameworks are also highlighted. Finally, a perspective of synthetic porous framework studies on CT performance is provided along with some comparisons.

Construction of Cs2AgBiCl6/COF Heterojunction for Boosted Photocatalytic Thioester Oxidation.

Lead-free halide perovskites as a new kind of potential candidate for photocatalytic organic synthesis have attracted much attention recently. The rational heterojunction construction is regarded as an efficient strategy to delicately regulate their catalytic performances. Herein, a semi-conductive covalent organic framework (COF) nanosheet, C4N, is employed as the functional component to construct Cs2AgBiCl6/C4N (CABC/C4N) heterojunction. It is found that the C4N nanosheets with rich surface functional groups can serve as heterogeneous nucleation sites to manipulate the growth of CABC nanocrystals and afford close contact between each other, therefore facilitate the transfer and spatial separation of photogenerated charge carriers, as verified by in situ X-ray photoelectronic spectroscopy and Kelvin probe force microscopy. Moreover, the oxygen affinity of C4N endows the heterojunctions with outstanding aerobic reactivity, thus improving the photocatalytic performance largely. The optimal CABC/C4N heterojunction delivers a thioanisole conversion efficiency of 100% after 6 h, which is 2.2 and 7.7-fold of that of CABC and C4N. This work provides a new ideal for the design and application of lead-free perovskite heterojunction photocatalysts for organic reactions.

Robust Amide-Linked Fluorinated Covalent Organic Framework for Long-Term Oxygen Reduction Reaction Electrocatalysis.

The high energy demand of the evolving world opens the door to develop more sustainable and environmentally friendly energy sources. Oxygen reduction reaction (ORR) is a promising candidate, being the 2e- pathway of great interest for the green production of hydrogen peroxide. Metal-free covalent organic frameworks (COFs) electrocatalysts present a suitable alternative to substitute the noble-metals more commonly employed in this application. However, the lability of the linkages building up the framework raises an issue for their long-term use and application in aggressive media. Herein, a stable amide-linked COF is reported through post-synthetic modification of a previously reported imine-linked COF proven to be effective as an electrocatalyst, enhancing its chemical stability and electrochemical response. It is found that after the linkage transformation, the new electrocatalyst displays a higher selectivity toward the H2O2 production (98.5%) and an enhanced turnover frequency of 0.155 s-1, which is among the bests reported to date for metal-free and COF based electrocatalysts. The results represent a promising step forward for metal-free non pyrolyzed electrocatalysts, improving their properties through post-synthetic linkage modification for long-term operation.

Reticular Heterojunction for Organic Photoelectrochemical Transistor Detection of Neuron-Specific Enolase.

Reticular heterojunctions on the basis of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have sparked considerable interest in recent research endeavors, which nevertheless have seldom been studied in optoelectronic biosensing. In this work, its utilization for organic photoelectrochemical transistor (OPECT) detection of the important cancer biomarker of neuron-specific enolase (NSE) is reported. A MOF@COF@CdS quantum dots (QDs) heterojunction is rationally designed to serve as the photogating module against the polymeric channel. Linking with a sandwich complexing event, target-dependent alternation of the photogate is achieved, leading to the changed photoelectric conversion efficiency as indicated by the amplified OPECT signals. The proposed assay demonstrates good analytical performance in detecting NSE, featuring a linear detection range from 0.1 pg mL-1 to 100 ng mL-1, with a detection limit of 0.033 pg mL-1.

Copper Dispersed Covalent Organic Framework for Azide-Alkyne Cycloaddition and Fast Synthesis of Rufinamide in Water.

A crystalline porous bipyridine-based Bpy-COF with a high BET surface area (1864 m2 g-1) and uniform mesopore (4.0 nm) is successfully synthesized from 1,3,5-tris-(4'-formyl-biphenyl-4-yl)triazine and 5,5'-diamino-2,2'-bipyridine via a solvothermal method. After Cu(I)-loading, the resultant Cu(I)-Bpy-COF remained the ordered porous structure with evenly distributed Cu(I) ions at a single-atom level. Using Cu(I)-Bpy-COF as a heterogeneous catalyst, high conversions for cycloaddition reactions are achieved within a short time (40 min) at 25 °C in water medium. Moreover, Cu(I)-Bpy-COF proves to be applicable for aromatic and aliphatic azides and alkynes bearing various substituents such as ester, hydroxyl, amido, pyridyl, thienyl, bulky triphenylamine, fluorine, and trifluoromethyl groups. The high conversions remain almost constant after five cycles. Additionally, the antiepileptic drug (rufinamide) is successfully prepared by a simple one-step reaction using Cu(I)-Bpy-COF, proving its practical feasibility for pharmaceutical synthesis.

Aminal-Linked Covalent Organic Framework Membranes Achieve Superior Ion Selectivity.

High-salinity wastewater treatment is perceived as a global water resource recycling challenge that must be addressed to achieve zero discharge. Monovalent/divalent salt separation using membrane technology provides a promising strategy for sulfate removal from chlor-alkali brine. However, existing desalination membranes often show low water permeance and insufficient ion selectivity. Herein, an aminal-linked covalent organic framework (COF) membrane featuring a regular long-range pore size of 7 Å and achieving superior ion selectivity is reported, in which a uniform COF layer with subnanosized channels is assembled by the chemical splicing of 1,4-phthalaldehyde (TPA)-piperazine (PZ) COF through an amidation reaction with trimesoyl chloride (TMC). The chemically spliced TPA-PZ (sTPA-PZ) membrane maintains an inherent pore structure and exhibits a water permeance of 13.1 L m-2 h-1 bar-1, a Na2SO4 rejection of 99.1%, and a Cl-/SO4 2- separation factor of 66 for mixed-salt separation, which outperforms all state-of-the-art COF-based membranes reported. Furthermore, the single-stage treatment of NaCl/Na2SO4 mixed-salt separation achieves a high NaCl purity of above 95% and a recovery rate of ≈60%, offering great potential for industrial application in monovalent/divalent salt separation and wastewater resource utilization. Therefore, the aminal-linked COF membrane developed in this work provides a new research avenue for designing smart/advanced membrane materials for angstrom-scale separations.

A New Porphyrin-based Covalent Organic Framework with High Iodine Capture Capacity and I-doping Enhanced Conductivity.

Covalent organic frameworks (COFs) are porous organic materials with well-defined and uniform structure. The material is an excellent candidate as a solid adsorbent for iodine adsorption. In the present study, we report the synthesis of COF with porphyrin moiety, TF-TA-COF, by solvothermal reaction, which was characterized by XRD, solid-state 13 C NMR, IR, TGA, and nitrogen adsorption-desorption analysis. TF-TA-COF showed a high specific surface area of 443 m2 g-1 , and exhibited good adsorption performance for iodine vapor, with an adsorption capacity of 2.74 g g-1 . XPS and Raman spectrum indicated that a hybrid of physisorption and chemisorption took place between host COF and iodine molecules. The electric properties of iodine-loaded TF-TA-COF were also studied. After doped with iodine, the conductivity of the material increased by more than 5 orders of magnitude. The photoconductivity of I2 -doped COF was also studied and TF-TA-COF showed doping-enhanced photocurrent generation.

Construction of Multifunctional Covalent Organic Frameworks for Photocatalysis.

Covalent organic frameworks (COFs) have recently drawn intense attention due to their potential applications in photocatalysis. Herein, we report a multifunctional COF which consists of triphenylamine (TPA) and 2,2'-bipyridine (2, 2'-bipy) entities. The obtained TAPA-BPy-COF is a heterogeneous photocatalyst and can efficiently catalyze the oxidative coupling of thiols to disulfides. In addition, TAPA-BPy-COF can be further metalated by Pd(II) via 2,2'-bipy-metal coordination. The generated Pd@TAPA-BPy-COF can highly promote photocatalytic synthesis of 3-cyanopyridines via cascade addition/cyclization of arylboronic acids with γ-ketodinitriles in heterogeneous way. This work has demonstrated the way for the rational design and preparation of more efficient photoactive COFs for photocatalysis.

Copper-surface-mediated synthesis of sp2 carbon-conjugated covalent organic framework photocathodes for photoelectrochemical hydrogen evolution.

Sp2-carbon (sp2-c) covalent organic frameworks (COFs), featuring distinctive π-conjugated network structures, facilitate the migration of photo-generated carriers, rendering them exceptionally appealing for applications in photoelectrochemical water splitting. However, owing to the powdery nature of COFs, leaving anchor the sp2-c COFs powder tightly onto a conductive substrate challenging. Here, we propose a method for preparing photoactive substance-conductive substrate integrated photocathodes through copper surface-mediated knoevenagel polycondensation (Cu-SMKP), this approach results in a uniform and stable sp2-c COF film, directly grown on commercial copper foam (COFTh-Cu). The COFTh-Cu demonstrates a high H2-evolution photocurrent density of 56 µA cm-2 at 0.3 V versus RHE, sustaining stability for 12 hours. The as-prepared COFTh-Cu represents a 4.5-fold increase in current density compared to traditional spin-coating methods and outperforms most COF photocathodes without cocatalysts. This innovative copper surface-mediated approach for preparing photocathodes opens up a crucial pathway towards the realization of highly active COF photocathodes.

Hydrophilic materials based on hydrogel polymers for enrichment of glycopeptides from serum of colorectal cancer patients.

In this work, a composite hydrogel material consisting of chitosan-based composite hydrogel was prepared by a simple and rapid synthetic method and will be named three-dimensional (3D)-IL-COF-1@CS hydrogel. Possessing a stable 3D network structure and outstanding hydrophilicity, the novel hydrogel is capable of capturing glycopeptides. The 3D-IL-COF-1@CS hydrogel showed good sensitivity (0.1 fmol/µL) and selectivity (1:2000). In addition, 19 glycopeptides were captured in standard samples. In the analysis of human serum, 148 glycopeptides assigned to 72 glycoproteins were assayed in the serum of normal individuals, and 245 glycopeptides corresponding to 100 glycoproteins were found in the serum of colorectal cancer (CRC) patients. More importantly, several functional programs based on Gene Ontology analysis supported molecular biological processes that may be relevant to the pathogenesis of CRC, including aging, fibrinogen complex, and arylesterase activity. The low cost, simplicity, rapid synthesis, and good enrichment performance have a great future in glycoproteomics analysis and related diseases.

Hydroxylated hierarchical flower-like COF for solid-phase extraction of adrenergic receptor agonists in milk.

A new detection platform based on a hydroxylated covalent organic framework (COF) integrated with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was constructed and used for detecting adrenergic receptor agonists (ARAs) residues in milk. The hydroxylated COF was prepared by polymerization of tris(4-aminophenyl)amine and 1,3,5-tris(4-formyl-3-hydroxyphenyl)benzene and applied to solid-phase extraction (SPE) of ARAs. This hydroxylated COF was featured with hierarchical flower-like morphology, easy preparation, and copious active adsorption sites. The adsorption model fittings and molecular simulation were applied to explore the potential adsorption mechanism. This detection platform was suitable for detecting four α2- and five ß2-ARAs residues in milk. The linear ranges of the ARAs were from 0.25 to 50 µg·kg-1; the intra-day and the inter-day repeatability were in the range 2.9-7.9% and 2.0-10.1%, respectively. This work demonstrates this hydroxylated COF has great potential as SPE cartridge packing, and provides a new way to determine ARAs residues in milk.

Multiple Impact-Resistant 2D Covalent Organic Framework.

Exploring and designing two-dimensional (2D) nanomaterials for armor-piercing protection has become a research focus. Here, by molecular dynamics simulation, we revealed that the ultralight monolayer covalent organic framework (COF), one kind of novel 2D crystalline polymer, possesses superior impact-resistant capability under high-velocity impact. The calculated specific penetration energy is much higher than that of other traditional impact-resistant materials, such as steel, poly(methyl methacrylate), Kevlar, etc. It was found that the hexagonal nanopores integrated by polymer chains have large deformation compatibility resulting from flexible torsion and stretching, which can remarkably contribute to the energy dissipation. In addition, the deformable nanopores can effectively restrain the crack propagation, enable COF to resist multiple impacts. This work uncovers the extreme dynamic responses of COF under high-velocity impact and provides theoretical guidance for designing superstrong 2D polymer-based crystalline nanomaterials.

Child-oriented family therapy in China: A cross-cultural application of integrative family therapy targeting children aged 4-10.

This article describes child-oriented family therapy (COF), a family therapy approach to early psychological and behavioral problems that is widely applied in northern Europe and has been adopted by countries with different cultures, such as Germany and China. This article explains the theoretical background, setting, characteristics, development and effective factors of this method and explores relevant research. In addition, the application of this method in China and reflections on its applicability to families in different cultures are presented. A clinical case is provided to illustrate the core therapeutic principles of COF. Since the application of COF interventions to families with children in Asian cultures remains understudied, the widespread availability of COF and adaptation to local conditions could facilitate training and research achievements in this field.

Fabrication of Active Z-Scheme Sr2MgSi2O7: Eu2+, Dy3+/COF Photocatalyst for Round-the-Clock Efficient Removal of Total Cr.

Photoreduction is recognized as a desirable treatment method for hexavalent chromium (Cr(VI)). However, it has been limited by the intermittent solar flux and limited light absorption. In this work, a novel Z-scheme photocatalyst combining a covalent organic framework (COF) with Eu2+, Dy3+ co-doped Sr2MgSi2O7 (Sr2MgSi2O7:Eu2+, Dy3+) is synthesized, which shows the high spectral conversion efficiency and works efficiently in both light irradiation and dark for Cr(VI) reduction. Sr2MgSi2O7:Eu2+, Dy3+ serves as both an electron transfer station and active sites for COF molecule activation, thus resulting in 100% photoreduction of Cr(VI) (50 mL, 10 mg/L) with high light stability and over 1 h dark activity. Moreover, the XPS and FT-IR analyses reveal the existence of functional groups (Si-OH on Sr2MgSi2O7:Eu2+, Dy3+, and -NH- on COFTP-TTA) on the composited catalyst as active sites to adsorb the resultant Cr(III) species, demonstrating a synergistic effect for total Cr removal. This work provides an alternative method for the design of a round-the-clock photocatalyst for Cr(VI) reduction, allowing a versatile solid surface activation for establishing a more energy efficient and robust photocatalysis process for Cr pollution cleaning.

Aus Klinik und Praxis / From Clinic and Practice. Kinderorientierte Familientherapie (KOF) in China: ein Fallbericht.

Child-Oriented FamilyTherapy (COF) in China: A Case Study Chinese families with children aged four to ten years need effective intervention approaches. This case study of a family with a child with early emotional and behavioural problems describes the approach of child-oriented family therapy (COF). After a brief introduction to the principles and framework of COF, the procedure is illustrated using the case study. It is shown that COF can be a particularly suitable therapeutic approach for families with children aged four to ten. Finally, the application of COF in China with cultural differences is discussed.

Efficient Capture and Low Energy Release of NH3 by Azophenol Decorated Photoresponsive Covalent Organic Frameworks.

In NH3 capture technologies, the desorption process is usually driven by high temperature and low pressure (such as 150-200 °C under vacuum), which accounts for intensive energy consumption and CO2 emission. Developing light responsive adsorbent is promising in this regard but remains a great challenge. Here, we for the first time designed and synthesized a light responsive azophenol-containing covalent organic framework (COF), COF-HNU38, to address this challenge. We found that at 25 °C and 1.0 bar, the cis -COF exhibited a NH3 uptake capacity of 7.7 mmol g-1 and a NH3/N2 selectivity of 158. In the adsorbed NH3, about 29.0 % could be removed by vis-light irradiated cis-trans isomerization at 25 °C, and the remaining NH3 might be released at 25 °C under vacuum. Almost no decrease in adsorption capacity was observed after eight adsorption-desorption cycles. As such, an efficient NH3 capture and low energy release strategy was established thanks to the multiple hydrogen bond interactions (which are strong in total but weak in individuals) between NH3 and the smart COF, as well as the increased polarity and number of hydrogen bond sites after the trans-cis isomerization.