Structural Regulation of Covalent Organic Frameworks for Catalysis

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(8), P. 1214 - 1226

Published: March 29, 2024

ConspectusChemical reactions can be promoted at lower temperatures and pressures, thereby reducing the energy input, by introducing suitable catalysts. Despite its significance, quest for efficient stable catalysts remains a significant challenge. In this context, addressing efficiency of stands out as paramount concern. However, challenges posed vague structure limited tailorability traditional would make it highly desirable to fabricate optimized based on understanding structure–activity relationships. Covalent organic frameworks (COFs), subclass fully designed crystalline materials formed polymerization building blocks through covalent bonds have garnered widespread attention in catalysis. The precise customizable structures COFs, coupled with attributes such high surface area facile functional modification, COFs attractive molecular platforms catalytic applications. These inherent advantages position ideal catalysts, facilitating elucidation structure-performance relationships further improving Nevertheless, there is lack systematic emphasis summary structural regulation atomic/molecular level COF Consequently, growing need summarize research field provide deep insights into COF-based catalysis promote development.In Account, we will recent advances achieved placing an design enhanced Considering unique components present fundamental principles rational This Account starts presenting overview explaining why are promising Then, introduce principle Next, following three aspects specific strategies catalysts: (1) By designing different groups integrating metal species unit, activity and/or selectivity finely modulated. (2) Regulating linkage facilitates charge transfer modulates electronic sites, accordingly, intrinsic activity/selectivity improved. (3) means pore wall/space engineering, microenvironment surrounding sites modulated optimize performance. Finally, current future developments discussed detail. provides insight toward their performance, which inspiration other heterogeneous

Language: Английский

---

Glucose oxidase: An emerging multidimensional treatment option for diabetic wound healing

Bioactive Materials, Journal Year: 2024, Volume and Issue: 44, P. 131 - 151

Published: Oct. 15, 2024

Language: Английский

---

Nanoencapsulation of Living Microbial Cells in Porous Covalent Organic Framework Shells

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Encapsulating living cells within nanoshells offers an important approach to enhance their stability against environmental stressors and broaden application scope. However, this often leads impaired mass transfer at the cell biointerface. Strengthening protective shell with well-defined, ordered transport channels is crucial regulating molecular maintaining viability biofunctionality. Herein, we report construction of covalent organic framework (COF) mesoporous shells for single-cell nanoencapsulation, providing selective permeability comprehensive protection microbial cells. The COF ensure nutrient uptake while blocking large harmful molecules UV-C radiation, thereby preserving metabolic activity. Integration such crystalline porous genetically modified factories production further investigated, revealing no adverse effects, as demonstrated by riboflavin production. Moreover, effectively shields cells, ensuring efficient bioproduction even after being treated under harsh conditions. This versatile encapsulation applicable different types, a robust platform surface engineering.

Language: Английский

---

Electrostatic polarity-regulated, vinylene-linked cationic covalent organic frameworks as an ionic sieve membrane for long-cyclable lithium-sulfur batteries

Energy storage materials, Journal Year: 2024, Volume and Issue: 66, P. 103222 - 103222

Published: Feb. 1, 2024

Language: Английский

---

Covalent Organic Frameworks Based Photoenzymatic Nano‐reactor for Asymmetric Dynamic Kinetic Resolution of Secondary Amines

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 17, 2024

Abstract Bio‐catalysis represents a highly efficient and stereoselective method for the synthesis of valuable chiral compounds, however, poor stability limited reaction types free enzymes restrict their wide application in industrial production. In this work, to overcome these problems, multifunctional photoenzymatic nanoreactor CALB@COF‐Ir was developed through encapsulation Candida antarctica lipase B (CALB) photosensitive covalent organic framework COF‐Ir . This bio‐nanocluster serves as catalysts asymmetric dynamic kinetic resolution (DKR) secondary amines give series high yields (up 99 %) enantioselectivities % ee). The well‐designed not only acts safety cover prevent CALB from deactivation but promotes racemization via photo‐induced hydrogen atom transfer (HAT) process. Photoelectric characterization TDDFT calculation revealed that (ppy) 2 Ir units play crucial role photocatalytic system which enhance its photo‐redox properties facilitating separation between photoelectrons (e − ) holes (h + ). Furthermore, heterogeneous could be recycled five rounds with slight decline catalytic reactivity.

Language: Английский

---

Enzyme Immobilization using Covalent Organic Frameworks: From Synthetic Strategy to COFs Functional Role

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(31), P. 40371 - 40390

Published: July 29, 2024

Enzymes, a class of biocatalysts, exhibit remarkable catalytic efficiency, specificity, and selectivity, governing many reactions that are essential for various cascades within living cells. The immobilization structurally flexible enzymes on appropriate supports holds significant importance in facilitating biomimetic transformations extracellular environments. Covalent organic frameworks (COFs) have emerged as ideal candidates enzyme due to high surface tunability, diverse chemical/structural designs, exceptional stability, metal-free nature. Various techniques been proposed fabricate COF-enzyme biocomposites, offering enhancements activity reusability COF-immobilized well new insights into developing advanced enzyme-based applications. In this review, we provide comprehensive overview state-of-the-art strategies immobilizing COFs by focusing their applicability versatility. These systematically summarized compared categorizing them postsynthesis situ immobilization, where respective strengths limitations thoroughly discussed. Combined with an critical emerging applications, further elucidate the multifaceted roles subsequent highlighting biofunctionality achievable through COFs.

Language: Английский

---

Amphiphilic Covalent Organic Framework Nanoparticles for Pickering Emulsion Catalysis with Size Selectivity

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 1, 2024

Abstract Exploiting advanced amphiphilic solid catalysts is crucial to the development of Pickering emulsion catalysis. Herein, covalent organic framework (COF) nanoparticles constructed with highly hydrophobic monomers as linkers were found show superior amphiphilicity and they then developed a new class emulsifiers for Employing COFs emulsifiers, emulsions controllable type droplet sizes obtained. COF materials have also been demonstrated serve porous surface coatings replace traditional modifications stabilizing emulsions. After implanting Pd into COFs, obtained catalyst displayed 3.9 times higher catalytic efficiency than in biphasic oxidation reaction alcohols. Such an enhanced activity was resulted from high area regular structure COFs. More importantly, because their tunable pore diameters, catalysis remarkable size selectivity achieved. This work first example that applied catalysis, providing platform exploring frontiers

Language: Английский

---

Covalent organic frameworks for antibacterial applications

Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: 5(3), P. 101845 - 101845

Published: Feb. 26, 2024

Covalent organic frameworks (COFs) have emerged as an important material for antimicrobial applications due to their customizable porous structures, abundant active sites, and good stability. In this perspective, we explore the topological connectivity in construction of currently developed COFs, which mainly include –B–O–, –N–H–, β-ketoenamine, azine/triazine. The advantages pristine COFs mono- synergistic antimicrobials are integrated discussed. We further summarize COF-embedded hybrid materials, such COFs/metal nanoparticles, COFs/metal-organic frameworks, COFs/carbon COFs/other demonstrate diverse design application concepts. Finally, outline challenges promising prospects COF materials biomedical industrial fields, emphasizing need these from a multidimensional perspective.

Language: Английский

---

Precision Engineering of the Co‐immobilization of Enzymes for Cascade Biocatalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: April 1, 2024

Abstract The design and orderly layered co‐immobilization of multiple enzymes on resin particles remain challenging. In this study, the SpyTag/SpyCatcher binding pair was fused to N‐terminus an alcohol dehydrogenase (ADH) aldo‐keto reductase (AKR), respectively. A non‐canonical amino acid (ncAA), p ‐azido‐L‐phenylalanine (p‐AzF), as anchor for covalent bonding enzymes, genetically inserted into preselected sites in AKR ADH. Employing two bioorthogonal counterparts azide–alkyne cycloaddition immobilization ADH enabled sequential dual‐enzyme coating porous microspheres. ordered reactor subsequently used synthesize ( S )‐1‐(2‐chlorophenyl)ethanol asymmetrically from corresponding prochiral ketone, enabling situ regeneration NADPH. exhibited a high catalytic conversion 74 % good reproducibility, retaining 80 its initial activity after six cycles. product had 99.9 ee, which that maintained each cycle. Additionally, double‐layer method significantly increased enzyme loading capacity, approximately 1.7 times greater than traditional single‐layer immobilization. More importantly, it simultaneously both purification carriers, thus providing convenient approach facilitate cascade biocatalysis.

Language: Английский

---

An enzymatic continuous-flow reactor based on a pore-size matching nano- and isoporous block copolymer membrane

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 17, 2024

Abstract Continuous-flow biocatalysis utilizing immobilized enzymes emerged as a sustainable route for chemical synthesis. However, inadequate biocatalytic efficiency from current flow reactors, caused by non-productive enzyme immobilization or enzyme-carrier mismatches in size, hampers its widespread application. Here, we demonstrate general-applicable and robust approach the fabrication of high-performance enzymatic continuous-flow reactor via integrating well-designed scalable isoporous block copolymer (BCP) membranes carriers with an oriented productive employing material binding peptides (MBP). Densely packed uniform enzyme-matched nanochannels BCP endow desired nanoconfined environments towards phytase. Tuning nanochannel properties can further regulate complex reaction process fortify catalytic performance. The synergistic design efficient empowers excellent performance >1 month operational stability, superior productivity, high space-time yield (1.05 × 10 5 g L −1 d ) single-pass process. obtained makes designed nano- membrane highly attractive industrial applications.

Language: Английский

---