Covalent Polymerization Research Articles

Mild and Subtle Synthesis of β-Ketoenamine COFs with High Crystallinity and Controllable Solubility Guided by a Monomer Preassembly Strategy.

The stability of covalent organic frameworks (COFs) is crucial for their applications in demanding environments. However, increasing the stability of COFs often comes with challenges such as higher synthesis difficulty, lower crystal quality, and reduced controllability during synthesis, making it difficult to regulate dimensions and morphology, thereby impacting the processing and shaping of stable COFs. Herein, the study presents a novel confined polymerization approach guided by hydrogen bonding preassembly to synthesize a soluble and stable COF featuring β-ketoenamine linkage. The presence of relatively weaker hydrogen bonds accelerates the orderly arrangement of monomers, ensuring appropriate spacing, and orientations among functional groups. This facilitates efficient covalent polymerization, leading to the creation of the framework while minimizing the "self-correction" mechanism during crystal growth, thereby enhancing the efficiency of COF synthesis. Furthermore, this method offers precise control over the size of the synthesized COF. The resulting crystalline COF can be toggled between dissolution and precipitation states, facilitating the fabrication of mixed matrix membranes (MMMs) through leveraging the solubility properties of COF. Overall, this pioneering strategy yields valuable insights for advancing weak bond assembly-mediated confined polymerization approaches, the controlled synthesis of stable COFs, and the preparation and processing of soluble COFs in diverse applications.

Inverse Vulcanization of Vinyl-polycyclic Aromatic Hydrocarbon Monomers and Dynamic Covalent Polymerization with Liquid Crystalline Monomers

Inverse Vulcanization of Vinyl-polycyclic Aromatic Hydrocarbon Monomers and Dynamic Covalent Polymerization with Liquid Crystalline Monomers

Template-assisted Flexible-to-rigid Transition of Peptides in Head-to-tail Self-polymerization Enables Sequence-controllable and Post-modifiable Peptide Nanofibers.

Peptide-based nanofibers are promising materials for many essential applications and can be generalized into two categories, self-assembling peptide nanofibers (SAPNs) and poly(amino acid) nanofibers (PAANs). Non-covalent SAPNs are sequence-controllable, but poorly stable and not suitable for post-modification. While covalent PAANs are post-modifiable, however, their sequences are either monotonic or undefined. The nanofibers obtained by head-to-tail covalent coupling polymerization of sequence-known peptides, which we call series-connected peptide nanofibers (SCPNs), promise to have the advantages of both SAPNs and PAANs, but they are barely reported. The undesired backbiting effect during the head-to-tail polymerization is one of the possible challenges. Here, we present a template-assisted strategy to trigger the flexible-to-rigid transition of peptide units, which can avoid the backbiting effect and enable consecutive intermolecular polymerization of peptides to produce desired sequence-controlled covalent SCPNs. SCPNs are highly stable and can function as excellent parent materials for various post-processing to create diverse hierarchical materials independent of the peptide sequence. Moreover, SCPNs allow for the display of predetermined functional groups at regular intervals along the nanofibers by pre-modification of the initial peptide sequence. SCPNs represent a new category of peptide-based nanofibers with outstanding performances and vast potential.

Aqueous‐Phase Preparation of Core–Shell Perovskite Nanorods Encapsulated in Polydopamine with Ultrahigh Water Stability

All‐inorganic perovskite CsPbBr3 (CPB) nanocrystals (NCs) are not widely applied in aqueous environments due to their readily decomposable nature. Therefore, the aqueous‐phase preparation of CPB NCs has been a considerable challenge. In this work, a feasible method is proposed for preparing aqueous‐phase core–shell CPB nanorods (NRs) encapsulated with polydopamine (PDA) by employing a multifunctional additive cesium trifluoroacetate (Cs‐TFA). Highly luminescent TFA‐CPB NRs are obtained via a chemical transformation of Cs4PbBr6 NCs in water. Subsequently, PDA constitutes a robust shell on the surface of TFA‐CPB NRs through the covalent oxidative polymerization, which effectively reduces the original dynamic properties of surface ligands, retards the decomposition of ligands and inhibits the leakage of Pb2+ ions. The results demonstrate that the fluorescence intensity of TFA‐CPB@PDA NRs maintains 49.3% of the initial intensity after 136 days. Meanwhile, the NRs exhibit low cytotoxicity, and the cell viability remains at 80% when the concentration of the NRs is 200 μg mL−1. The reliable preparation of aqueous‐phase core–shell perovskite NRs (PNRs) will facilitate their development in many fields, such as materials science, biology, medicine, and their applications in aqueous environments.

Construction of Benzoxazine-linked One-Dimensional Covalent Organic Frameworks Using the Mannich Reaction.

Covalent polymerization of organic molecules into crystalline one-dimensional (1D) polymers is effective for achieving desired thermal, optical, and electrical properties, yet it remains a persistent synthetic challenge for their inherent tendency to adopt amorphous or semicrystalline phases. Here we report a strategy to synthesize crystalline 1D covalent organic frameworks (COFs) composing quasi-conjugated chains with benzoxazine linkages via the one-pot Mannich reaction. Through [4+2] and [2+2] type Mannich condensation reactions, we fabricated stoichiometric and sub-stoichiometric 1D covalent polymeric chains, respectively, using doubly and singly linked benzoxazine rings. The validity of their crystal structures has been directly visualized through state-of-the-art cryogenic low-dose electron microscopy techniques. Post-synthetic functionalizations of them with a chiral MacMillan catalyst produce crystalline organic photocatalysts that demonstrated excellent catalytic and recyclable performance in light-driven asymmetric alkylation of aldehydes, affording up to 94 % enantiomeric excess.

Strategic design of magnetic ionic covalent organic frameworks incorporating amino acid ionic liquids for enhanced selectivity adsorption of benzimidazoles

Advancing the frontier of material design, our innovative magnetic ionic covalent organic framework (MiCOF) masterfully overcomes traditional barriers in selective adsorption, pioneering new functionalities and surface engineering techniques to effectively target and mitigate the impacts of benzimidazoles (BZDs). In previous studies, the idea of designing magnetic nanomaterials through theoretical screening of ionic liquids has been successfully proposed. This work proposed a theoretical and practical design for MiCOFs, aimed at providing a sensitive, selective, rapid, and straightforward method for analyzing trace substances in complex biological matrices. In a gentle one-pot process, the surface of Fe3O4 was coated with covalent organic frameworks (COFs) layer, followed by the modification with amino acid ionic liquid (AAIL) through covalent radical polymerization, facilitated by the abundant unsaturated vinyl groups present. This resulted in MiCOFs (Fe3O4@COF-AAIL) with a stable structure. Compared to unmodified Fe3O4@COF, Fe3O4@COF-AAIL exhibited excellent adsorption selectivity for BZDs. This enhanced selectivity is primarily due to the strong hydrogen bonds and π-π interactions between AAIL and BZDs, aligning well with COSMO-RS theoretical screening predictions. The development of magnetic dispersive solid-phase extraction (MDSPE) enabled rapid processing of BZDs in plasma with low matrix effects (0.9–1.3). This study not only validates a robust framework for the selective separation of trace contaminants in complex biological matrices but also advances the design and application of MiCOFs, setting a new paradigm in material science that could transform the design of novel materials for specific tasks.

Bio-inspired co-deposition of dopamine and N-oxide zwitterionic polyethyleneimine to fabricate anti-fouling loose nanofiltration membranes for dye desalination

Developing anti-fouling loose nanofiltration membranes (LNMs) that can achieve dye desalination of saline textile wastewater through dye retention and salt permeation for resource utilization remains an urgent challenge that needs to be addressed. Inspired by the biomimetic adhesion of mussels and the excellent fouling resistance of saltwater fish surfaces, novel LNMs were prepared through co-deposition strategy using dopamine (DA) and N-oxide zwitterionic polyethyleneimine (ZPEI) as biomimetic functional materials. There are multiple interactions between them, including Schiff base reaction, Michael addition reaction, cation-π interaction and covalent polymerization. Compared with PEI-LNM prepared under the similar method, the optimized ZPEI-LNM displays more uniform surface, smaller average roughness (6 nm vs 22 nm), and denser pore size (0.69 nm vs 0.79 nm), indicating the zwitterionic N-oxide moieties in ZPEI regulate the deposition process and the cross-linking structure of the selective layer. ZPEI-LNM exhibits a high pure water flux of 203.0 L m−2h−1 under 0.6 MPa. Importantly, ZPEI-LNM shows high retention towards different dyes, including Congo red (CR, negative, 696.8 g/mol) of 100.0 %, Acid fuchsin (AF, negative, 585.5 g/mol) of 99.5 %, Crystalline violet (CV, positive, 408.0 g/mol) of 98.2 %, and Indigo carmine (negative, 466.4 g/mol) of 96.0 %, while the rejection of NaCl (8.7 %) and Na2SO4 (12.7 %) are both lower. As expected, for the mixture solution of AF/NaCl, the dyes are efficiently rejected, while salts can pass through, indicating that ZPEI-LNM displays an excellent dye desalination capability. Furthermore, multiple-cycle antifouling tests for bovine serum albumin (BSA) and sodium alginate (SA) reveal that the flux recovery ratios are higher than those of PEI-LNM (BSA: 90.4 % vs 81.9 %; SA: 86.6 % vs 80.5 %), indicating ZPEI-LNM exhibits better anti-fouling performance towards different model foulants owing to the outstanding hydration layer caused by zwitterionic N-oxide moieties and lower surface roughness. Consequently, the work offers a new viewpoint for the fabrication of anti-fouling LNMs via biomimetic strategy for dye desalination.

Molecular basis for dual functions in pilus assembly modulated by the lid of a pilus-specific sortase

The biphasic assembly of Gram-positive pili begins with the covalent polymerization of distinct pilins catalyzed by a pilus-specific sortase, followed by the cell wall anchoring of the resulting polymers mediated by the housekeeping sortase. In Actinomyces oris, the pilus-specific sortase SrtC2 not only polymerizes FimA pilins to assemble type 2 fimbriae with CafA at the tip, but it can also act as the anchoring sortase, linking both FimA polymers and SrtC1-catalyzed FimP polymers (type 1 fimbriae) to peptidoglycan when the housekeeping sortase SrtA is inactive. To date, the structure-function determinants governing the unique substrate specificity and dual enzymatic activity of SrtC2 have not been illuminated. Here, we present the crystal structure of SrtC2 solved to 2.10-Å resolution. SrtC2 harbors a canonical sortase fold and a lid typical for class C sortases and additional features specific to SrtC2. Structural, biochemical, and mutational analyses of SrtC2 reveal that the extended lid of SrtC2 modulates its dual activity. Specifically, we demonstrate that the polymerizing activity of SrtC2 is still maintained by alanine-substitution, partial deletion, and replacement of the SrtC2 lid with the SrtC1 lid. Strikingly, pilus incorporation of CafA is significantly reduced by these mutations, leading to compromised polymicrobial interactions mediated by CafA. In a srtA mutant, the partial deletion of the SrtC2 lid reduces surface anchoring of FimP polymers, and the lid-swapping mutation enhances this process, while both mutations diminish surface anchoring of FimA pili. Evidently, the extended lid of SrtC2 enables the enzyme the cell wall-anchoring activity in a substrate-selective fashion.

A novel covalent grafting method between cellulose and ferulic acid through HRP enzyme/acetylacetone/L-Ascorbic acid ternary dual initiator system

In the application of natural dyes, using environmentally and human body harmful metal dyes was still the mainstream dyeing method in the process of cellulose fiber dyeing with natural dyes. This study proposed a new method that can catalyzed the covalent grafting of cellulose materials with Ferulic acid (FA), the ternary system consisting of horseradish peroxidase (HRP), acetylacetone (ACAC) and L-Ascorbic acid (AA). The grafting process of cellulose materials with FA was systematically studied, and the optimal grafting polymerization conditions was determined using orthogonal experimental analysis. In the experiment, it was found that the morphology and structure of cellulose materials significantly affect their grafting polymerization performance with FA, and the change rule of their grafting rate was cotton fabric (3.84%) < cotton yarn (4.54%) < tencel fabric (4.70%) < tencel yarn (53.06%) < cotton cellulose (5.59%) < corn starch (6.70%). The grafted fabrics have excellent color fastness, antibacterial and UV resistance performance. Finally, the structural characteristics of cellulose and its analogues grafted with FA were characterized through FT-IR, 1H NMR, and the possible free radical covalent polymerization mechanism between cellulose materials and FA was analyzed.

Light-Induced Increase of the Local Molecular Coverage on a Surface.

Light is a versatile tool to remotely activate molecules adsorbed on a surface, for example, to trigger their polymerization. Here, we explore the spatial distribution of light-induced chemical reactions on a Au(111) surface. Specifically, the covalent on-surface polymerization of an anthracene derivative in the submonolayer coverage range is studied. Using scanning tunneling microscopy and X-ray photoemission spectroscopy, we observe a substantial increase of the local molecular coverage with the sample illumination time at the center of the laser spot. We find that the interplay between thermally induced diffusion and the reduced mobility of reaction products steers the accumulation of material. Moreover, the debromination of the adsorbed species never progresses to completion within the experiment time, despite a long irradiation of many hours.

High-strength and ultra-tough supramolecular polyamide spider silk fibers assembled via specific covalent and reversible hydrogen bonds

Achieving ultra-high tensile strength and exceptional toughness is a longstanding goal for structural materials. However, previous attempts using covalent and non-covalent bonds have failed, leading to the belief that these two properties are mutually exclusive. Consequently, commercial fibers have been forced to compromise between tensile strength and toughness, as seen in the differences between nylon and Kevlar. To address this challenge, we drew inspiration from the disparate tensile strength and toughness of nylon and Kevlar, both of which are polyamide fibers, and developed an innovative approach that combines specific intermolecular disulfide bonds and reversible hydrogen bonds to create ultra-strong and ultra-tough polyamide spider silk fibers. Our resulting Supramolecular polyamide spider silk, which has a maximum molecular weight of 1084 kDa, exhibits high tensile strength (1180 MPa) and extraordinary toughness (433 MJ/m3), surpassing Kevlar's toughness 8-fold. This breakthrough presents a new opportunity for the sustainable development of spider silk as an environmentally friendly alternative to synthetic commercial fibers, as spider silk is composed of amino acids. Future research could explore the use of these techniques and fundamental knowledge to develop other super materials in various mechanical fields, with the potential to improve people's lives in many ways. Statement of significance• By emulating synthetic commercial fibers such as nylon and polyethylene, we have successfully produced supramolecular-weight polyamide spider silk fibers with a molecular weight of 1084 kDa through a unique covalent bond-mediated linear polymerization reaction of spider silk protein molecules. This greatly surpasses the previous record of a maximum molecular weight of 556 kDa. • We obtained supramolecular polyamide spider silk fibers with both high-tensile strength and toughness. The stress at break is 1180 MPa, and the toughness is 8 times that of kevlar, reaching 433 MJ/m3. • Our results challenge the notion that it is impossible to manufacture fibers with both ultra-high tensile strength and ultra-toughness, and provide theoretical guidance for developing environmentally friendly and sustainable structural materials that meet industrial needs.

Sub-100 nm carriers by template polymerization for drug delivery applications.

Size-controlled drug delivery systems (DDSs) have gained significant attention in the field of pharmaceutical sciences due to their potential to enhance drug efficacy, minimize side effects, and improve patient compliance. This review provides a concise overview of the preparation method, advancements, and applications of size-controlled drug delivery systems focusing on the sub-100 nm size DDSs. The importance of tailoring the size for achieving therapeutic goals is briefly mentioned. We highlight the concept of "template polymerization", a well-established method in covalent polymerization that offers precise control over molecular weight. We demonstrate the utility of this approach in crafting a monolayer of a polymer around biomolecule templates such as DNA, RNA, and protein, achieving the generation of DDSs with sizes ranging from several tens of nanometers. A few representative examples of small-size DDSs that share a conceptual similarity to "template polymerization" are also discussed. This review concludes by briefly discussing the drug release behaviors and the future prospects of "template polymerization" for the development of innovative size-controlled drug delivery systems, which promise to optimize drug delivery precision, efficacy, and safety.

Covalent organic framework in-situ immobilized laccase for the covalent polymerization removal of sulfamethoxazole in the presence of natural phenols: Prominent enzyme stability and activity

In current water treatment processes, pollutants are typically degraded into small molecules and CO2 for detoxification. This study employed laccase-mediated aggregation of new pollutants with natural phenolic compounds to remove pollutants by forming large molecular substances, effectively sequestering carbon. Free laccase is susceptible to environmental influences, causing deactivation. However, immobilizing laccase onto a carrier enhances enzyme stability. In the experiment, laccase was immobilized onto the covalent organic framework TpPa-1 through an in-situ loading process, resulting in immobilized laccase Lac@TpPa-1. Stability studies revealed that immobilized laccase outperformed free laccase in terms of pH, temperature, and recyclability. Moreover, immobilized laccase was employed for catalyzing the removal of emerging pollutants containing natural phenolic compounds, achieving an 80.53% removal rate with the addition of 0.02 g of laccase within 5 h. Analytical techniques like Fourier-transform ion cyclotron resonance mass spectrometry were used to uncover reaction pathways, demonstrating the presence of radical polymerization and 1, 4 nucleophilic addition. This research utilized TpPa-1 as a carrier for laccase immobilization, promoting oxidation-induced polymerization for efficient pollutant removal. It provides a theoretical foundation for understanding the interplay between emerging pollutants and phenolic compounds in natural environments and enhances the practical application of laccase through immobilization.

Nucleic-Acid-Templated Synthesis of Smart Polymer Vectors for Gene Delivery.

Nucleic acids are information-rich and readily available biomolecules, which can be used to template the polymerization of synthetic macromolecules. Here, we highlight the control over the size, composition, and sequence one can nowadays obtain by using this methodology. We also highlight how templated processes exploiting dynamic covalent polymerization can, in return, result in therapeutic nucleic acids fabricating their own dynamic delivery vector - a biomimicking concept that can provide original solutions for gene therapies.

Cooperative Covalent Polymerization of N-carboxyanhydrides: from Kinetic Studies to Efficient Synthesis of Polypeptide Materials

ConspectusPolypeptides, as the synthetic analogues of natural proteins, are an important class of biopolymers that are widely studied and used in various biomedical applications. However, the preparation of polypeptide materials from the polymerization of N-carboxyanhydride (NCA) is limited by various side reactions and stringent polymerization conditions. Recently, we report the cooperative covalent polymerization (CCP) of NCA in solvents with low polarity and weak hydrogen-bonding ability (e.g., dichloromethane or chloroform). The polymerization exhibits characteristic two-stage kinetics, which is significantly accelerated compared with conventional polymerization under identical conditions. In this Account, we review our recent studies on the CCP, with the focus on the acceleration mechanism, the kinetic modeling, and the use of fast kinetics for the efficient preparation of polypeptide materials.By studying CCP with several initiating systems, we found that the polymerization rate was dependent on the secondary structure as well as the macromolecular architecture of the propagating polypeptides. The molecular interactions between the α-helical, propagating polypeptide and the monomer played an important role in the acceleration, which catalyzed the ring-opening reaction of NCA in an enzyme-mimetic, Michaelis–Menten manner. Additionally, the proximity between initiating sites further accelerated the polymerization, presumably due to the cooperative interactions of macrodipoles between neighboring helices and/or enhanced binding of monomers. A two-stage kinetic model with a reversible monomer adsorption process in the second stage was developed to describe the CCP kinetics, which highlighted the importance of cooperativity, critical chain length, binding constant, [M]0, and [M]0/[I]0. The kinetic model successfully predicted the polymerization behavior of the CCP and the molecular-weight distribution of resulting polypeptides.The remarkable rate acceleration of the CCP offers a promising strategy for the efficient synthesis of polypeptide materials, since the fast kinetics outpaces various side reactions during the polymerization process. Chain termination and chain transfer were thus minimized, which facilitated the synthesis of high-molecular-weight polypeptide materials and multiblock copolypeptides. In addition, the accelerated polymerization enabled the synthesis of polypeptides in the presence of an aqueous phase, which was otherwise challenging due to the water-induced degradation of monomers. Taking advantage of the incorporation of the aqueous phase, we reported the preparation of well-defined polypeptides from nonpurified NCAs. We believe the studies of CCP not only improve our understanding of biological catalysis, but also benefit the downstream studies in the polypeptide field by providing versatile polypeptide materials.

Structural Quantification of the Surface-Confined Metal-Organic Precursors Simulated with the Lattice Monte Carlo Method.

The diversity of surface-confined metal-organic precursor structures, which recently have been observed experimentally, poses a question of how the individual properties of a molecular building block determine those of the resulting superstructure. To answer this question, we use the Monte Carlo simulation technique to model the self-assembly of metal-organic precursors that precede the covalent polymerization of halogenated PAH isomers. For this purpose, a few representative examples of low-dimensional constructs were studied, and their basic structural features were quantified using such descriptors as the orientational order parameter, radial distribution function, and one- and two-dimensional structure factors. The obtained results demonstrated that the morphology of the precursor (and thus the subsequent polymer) could be effectively tuned by a suitable choice of molecular parameters, including size, shape, and intramolecular distribution of halogen substituents. Moreover, our theoretical investigations showed the effect of the main structural features of the precursors on the related indirect characteristics of these constructs. The results reported herein can be helpful in the custom designing and characterization of low-dimensional polymers with adjustable properties.

Structural and biochemical characterization of Clostridium perfringens pili protein B collagen-binding domains.

Sortase-mediated pili are flexible rod proteins composed of major and minor/tip pilins, playing important roles in the initial adhesion of bacterial cells to host tissues. The pilus shaft is formed by covalent polymerization of major pilins, and the minor/tip pilin is covalently attached to the tip of the shaft involved in adhesion to the host cell. The Gram-positive bacterium Clostridium perfringens has a major pilin, and a minor/tip pilin (CppB) with the collagen-binding motif. Here, we report X-ray structures of CppB collagen-binding domains, collagen-binding assays and mutagenesis analysis, demonstrating that CppB collagen-binding domains adopt an L-shaped structure in open form, and that a small β-sheet unique to CppB provides a scaffold for a favourable binding site for collagen peptide.

Latest advances in layered covalent organic frameworks for water and wastewater treatment

This review provides an overview of recent progress in the development of layered covalent organic frameworks (LCOFs) for the adsorption and degradation of pollutants in water and wastewater treatment. LCOFs have unique properties such as high surface area, porosity, and tunability, which make them attractive adsorbents and catalysts for water and wastewater treatment. The review covers the different synthesis methods for LCOFs, including self-assembly, co-crystallization, template-directed synthesis, covalent organic polymerization (COP), and solvothermal synthesis. It also covers the structural and chemical characteristics of LCOFs, their adsorption and degradation capacity for different pollutants, and their comparison with other adsorbents and catalysts. Additionally, it discussed the mechanism of adsorption and degradation by LCOFs, the potential applications of LCOFs in water and wastewater treatment, case studies and pilot-scale experiments, challenges, and limitations of using LCOFs, and future research directions. The current state of research on LCOFs for water and wastewater treatment is promising, however, more research is needed to improve their performance and practicality. The review highlights that LCOFs have the potential to significantly improve the efficiency and effectiveness of current water and wastewater treatment methods and can also have implications for policy and practice.

Recognition of “Oxygen-/Water-Fueled” PET-RAFT Protocol Matched to Covalent Organic Frameworks

The reactive oxygen species (ROS)-mediated photoinduced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) process is an attractive tool to enhance the oxygen tolerance of radical polymerization systems. In this paper, we investigate the relationship between the covalent organic framework (COF) structure and polymerization performance based on the O2•–/H2O system by modulating the COF at atomic and molecular levels. We combine density functional theory (DFT) calculations and experiments to clarify the “oxygen-/water-fueled” PET-RAFT polymerization mechanism and identify the key steps of the protocol. Based on the modulation of the TD-1 COF template structure, the relatively efficient charge–hole separation efficiency allows the matching of TD-2 COF and TD-3 COF with the O2•–/H2O system to achieve high-quality RAFT polymerization, providing insights into the rational design and development of catalytic systems with better performance.

Toward understanding the emergence of life: A dual function of the system of nucleotides in the metabolically closed autopoietic organization

General structure of metabolism includes the reproduction of catalysts that govern metabolism. In this structure, the system becomes autopoietic in the sense of Maturana and Varela, and it is closed to efficient causation as defined by Robert Rosen. The autopoietic maintenance and operation of the catalysts takes place via the set of free nucleotides while the synthesis of catalysts occurs via the information encoded by the set of nucleotides arranged in polymers of RNA and DNA. Both energy charge and genetic information use the components of the same pool of nucleoside triphosphates, which is equilibrated by thermodynamic buffering enzymes such as nucleoside diphosphate kinase and adenylate kinase. This occurs in a way that the system becomes internally stable and metabolically closed, which initially could be realized at the level of ribozymes catalyzing basic metabolic reactions as well as own reproduction. The function of ATP, GTP, UTP, and CTP is dual, as these species participate both in the general metabolism as free nucleotides and in the transfer of genetic information via covalent polymerization to nucleic acids. The changes in their pools directly impact both bioenergetic pathways and nucleic acid turnover. Here we outline the concept of metabolic closure of biosystems grounded in the dual function of nucleotide coenzymes that serve both as energetic and informational molecules and through this duality generate the autopoietic performance and the ability for codepoietic evolutionary transformations of living systems starting from the emergence of prebiotic systems.