Covalent Cross-linking Research Articles

Tough and highly stretchable multifunctional ionogels based on phase-separated structure and nanocellulose macromolecular covalent cross-linker

Tough and highly stretchable multifunctional ionogels based on phase-separated structure and nanocellulose macromolecular covalent cross-linker

Antimicrobial Hydrogels Based on Cationic Curdlan Derivatives for Biomedical Applications.

Hydrogels based on biocompatible polysaccharides with biological activity that can slowly release an active principle at the wound site represent promising alternatives to traditional wound dressing materials. In this respect, new hydrogels based on curdlan derivative with 2-hydroxypropyl dimethyl octyl ammonium groups (QCurd) and native curdlan (Curd) were obtained at room temperature by covalent cross-linking using a diepoxy cross-linking agent. The chemical structure of the QCurd/Curd hydrogels was investigated by Fourier transform infrared spectroscopy (FTIR) spectroscopy. Scanning electron microscopy (SEM) revealed well-defined regulated pores with an average diameter between 50 and 75 μm, and hydrophobic micro-domains of about 5 μm on the pore walls. The high swelling rate (21-24 gwater/ghydrogel) and low elastic modulus values (7-14 kPa) make them ideal for medical applications as wound dressings. To evaluate the possible use of the curdlan-based hydrogels as active dressings, the loading capacity and release kinetics of diclofenac, taken as a model drug, were studied under simulated physiological skin conditions. Several mathematical models have been applied to evaluate drug transport processes and to calculate the diffusion coefficients. The prepared QCurd/Curd hydrogels were found to have good antibacterial properties, showing a bacteriostatic effect after 48 h against S. aureus, MRSA, E. coli, and P. aeruginosa. The retarded drug delivery and antimicrobial properties of the new hydrogels support our hypothesis that they are candidates for the manufacture of wound dressings.

Tunicate cellulose nanocrystals strengthened injectable stretchable hydrogel as multi-responsive enhanced antibacterial wound dressing for promoting diabetic wound healing

The intricate microenvironment of diabetic wounds characterized by hyperglycemia, intense oxidative stress, persistent bacterial infection and complex pH fluctuations hinders the healing process. Herein, an injectable multifunctional hydrogel (QPTx) was developed, which exhibited excellent mechanical performance and triple responsiveness to pH, temperature, and glucose due to dynamic covalent cross-linking involving dynamic Schiff base bonds and phenylboronate esters with phenylboronic-modified quaternized chitosan (QCS-PBA), polydopamine coated tunicate cellulose crystals (PDAn@TCNCs) and polyvinyl alcohol (PVA). Furthermore, the hydrogels can incorporate insulin (INS) drugs to adapt to the complex and variable wound environment in diabetic patients for on-demand drug release that promote diabetic wound healing. Based on various excellent properties of the colloidal materials, the hydrogels were evaluated for self-healing, rheological and mechanical properties, in vitro insulin response to pH/temperature/glucose release, antibacterial, antioxidant, tissue adhesion, coagulation, hemostasis in vivo and in vitro, and biocompatibility and biodegradability. By introducing PDAn@TCNCs particles, the hydrogel has photothermal antibacterial activity, enhanced adhesion and oxidation resistance. We further demonstrated that these hydrogel dressings significantly improved the healing process compared to commercial dressings (Tegaderm™) in full-layer skin defect models. All indicated that the glucose-responsive QPTx hydrogel platform has great potential for treating diabetic wounds.

A novel multifunction of wearable ionic conductive hydrogel sensor for promoting infected wound healing

Conductive hydrogels have attracted widespread attention in applications of artificial biological tissues and ionic skin. Herein, a highly ionically conductive and biocompatibility hydrogels that integrate sensing, low swelling, and antimicrobial are prepared by the composition of chitosan (CS) chains, tannic acid (TA), polyacrylic acid (PAA), and metal cations. The hydrogels with high conductivity had tensile strain repeatable adhesion, wide strain detection, biocompatibility, and motion sensing capabilities. Particularly, in the aspect of hydrogel strain sensing based on ion conduction, it has high nonliearity (GF=2.05) with a large strain (20 %-1400 %), and excellent cycle stability. In addition, owing to the low-swelling effect and dipole-dipole interaction between the existence of free catechol groups of the zwitterionic group and TA in the zwitterionic sulfobetaine methacrylate (SBMA), the hydrogels display repeatable and controllable adhesiveness. Meanwhile, the covalent cross-linking between AA and SBMA synergistically enhances the mechanical properties of the hydrogels (169 kPa, 1474 %). Furthermore, as demonstrated in the L929 mouse wound infection model, the results indicated that the prepared hydrogel group had antimicrobial activity and reduced inflammation, thereby accelerating wound healing. The biocompatible and mutli-functional conductive hydrogels provide a new method for the design of novel type ionic skin device.

In situ growth of HKUST-1 on electrospun polyacrylonitrile nanofibers/regenerated cellulose aerogel for efficient methylene blue adsorption

Dyes, as organic pollutants, are causing increasingly severe environmental problems. Metal-organic frameworks (MOFs) are considered promising dye adsorbents; however, their application is limited due to their powder or solid particle forms and limited reusability. Therefore, this study proposes an innovative approach to develop a novel MOF-based composite aerogel, specifically a HKUST-1/polyacrylonitrile nanofibers/regenerated cellulose (HKUST-1/PANNs/RC) composite aerogel adsorbent, for the adsorption of pollutants in water. This adsorbent was successfully prepared using a simple method combining covalent crosslinking, quick freezing, freeze-drying, in-situ growth synthesis, and solvothermal techniques. The HKUST-1/PANNs/RC composite aerogel exhibits a significantly large specific surface area, which is approximately 64 times greater than that of PANNs/RC (10.45 m2·g−1), with a specific surface area of 669.9 m2·g−1. The PANNs serve as a support framework, imparting excellent mechanical properties to the composite aerogel, enhancing its overall stability and recoverability. Additionally, the composite aerogel contains numerous -COOH and -OH groups on its surface, providing strong acid resistance and facilitating interactions with pollutant molecules through electrostatic interactions, π-π conjugation, n-π* interactions, and hydrogen bonding, thereby promoting the adsorption process. Using methylene blue (MB) as a probe molecule, the study results demonstrate that the HKUST-1/PANNs/RC composite aerogel has an adsorption capacity of 522.01 mg·g−1 for MB (25 h), exhibiting excellent adsorption performance. This composite aerogel shows great potential for application in water pollution control.

Multiscale assessment of artificial aging treatment of polysaccharides from tonewood species

In the acoustics of musical instruments with a resonator body, the aging of the wood leads to the improvement of the acoustic properties due to increasing the crystallinity of wood. This phenomenon could be explained by the fact that wood is a complex product based on three-dimensional polymer chains of carbohydrates, its aging being closely related to covalent cross-linking and scission of polymer chains. The aim of this study was to evaluate at a multiscale the changes produced artificial aging of tone wood by measuring the acoustic, mechanical and chemical parameters. The spruce and maple wood samples were investigated before and after exposure to ultraviolet (UV) radiation, through the tensile test, the time-of-flight method (TOF), the analysis of the wood color and the determination of the chemical fingerprint through Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The obtained results showed that the effects of artificial aging are manifested at the chemical level where the crystallinity increases up to the acoustic level, depending on the wood species and their quality class. These results are relevant for musical instrument manufacturers to find treatments that lead to superior acoustic properties.

Highly Water‐Rich Robust Coating for Separating Immiscible Liquids Mixtures of Wide Range of Surface Tension Differences

AbstractDeveloping mechanically robust and chemically tolerant coatings that maintain a high water content remains an extremely challenging task to pursue to date. Here, an optimum reinforcement of a hollow nano‐clay i.e., halloysite in a dual crosslinked and interpenetrating polymeric network is introduced to yield a high (≈95 wt%) water content coating with an ability to improve toughness (9.9 ± 0.6 MJm−3 Vs. 0.5 ± 0.03 MJ m−3) of a deformable fibrous substrate. The association of covalent and physical crosslinking chemistries provides essential tolerance against exposures to diverse severe chemically complex conditions, including extremes of pH, seawater, river water, and organic solvents. High water content in the prepared hydrogel network endows a robust bio‐inspired underwater nonadhesive superoleophobicity with oil contact angle of 160.7 ± 0.2° and force of oil‐droplet adhesion of 8.7 ± 0.3 µN. This approach provides a liquid selective filtrating membrane with ultrahigh crude oil/water separation efficiency (99.7%), superior intrusion pressure (3.5 ± 0.4 kPa), relatively high separation flux (11,162 Lm−2 h−1), and the ability to perform even when the surface tension of aqueous phase is brought down to similar of oily phase. Moreover, a mixture of immiscible, non‐aqueous liquids having differences in surface tension below 2.5 mN m−1 is successfully separated.

Fully Physically Crosslinked PNIPAM Ionogels with High Mechanical Properties and Temperature‐Managed Adhesion Achieved by H2O/Ionic Liquid Binary Solvents

AbstractPoly(N‐isopropylacrylamide) (PNIPAM) gels change their volume and hydrophilicity in response to temperature stimulus in flexible actuators, flexible sensors, and energy storage management. However, traditional PNIPAM gels exhibit low mechanical properties and poor self‐recovery ability due to weak intermolecular (chain) interactions and necessary covalent crosslinking. Herein, a water/ionic liquid (H2O/IL) binary solvent system that provides additional hydrogen bonding and hydrophobic interactions as well as can significantly increase the solubility (up to 60 wt.%) of NIPAM is developed. The fully physically crosslinked PNIPAM ionogel is prepared by utilizing the H2O/IL binary solvent and exhibited excellent mechanical performances, rapid self‐recovery properties, and strong adhesion strength. In addition, the lower critical solution temperature of the PNIPAM ionogel can also be tuned over a wide range (37‐70 °C) by adjusting the IL ratio in the binary solvent. Furthermore, based on the temperature sensitivity and ionic conductivity of the PNIPAM ionogel, applications of PNIPAM ionogels in smart devices, temperature‐managed adhesion, and flexible sensing are demonstrated, respectively. This work improves various performances of PNIPAM gels by using the H2O/IL binary solvent to adjust non‐covalent interactions and provided new ideas for developing high‐performance temperature‐sensitive gels.

A bioadhesive pacing lead for atraumatic cardiac monitoring and stimulation in rodent and porcine models.

Current clinically used electronic implants, including cardiac pacing leads for epicardial monitoring and stimulation of the heart, rely on surgical suturing or direct insertion of electrodes to the heart tissue. These approaches can cause tissue trauma during the implantation and retrieval of the pacing leads, with the potential for bleeding, tissue damage, and device failure. Here, we report a bioadhesive pacing lead that can directly interface with cardiac tissue through physical and covalent interactions to support minimally invasive adhesive implantation and gentle on-demand removal of the device with a detachment solution. We developed 3D-printable bioadhesive materials for customized fabrication of the device by graft-polymerizing polyacrylic acid on hydrophilic polyurethane and mixing with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) to obtain electrical conductivity. The bioadhesive construct exhibited mechanical properties similar to cardiac tissue and strong tissue adhesion, supporting stable electrical interfacing. Infusion of a detachment solution to cleave physical and covalent cross-links between the adhesive interface and the tissue allowed retrieval of the bioadhesive pacing leads in rat and porcine models without apparent tissue damage. Continuous and reliable cardiac monitoring and pacing of rodent and porcine hearts were demonstrated for 2 weeks with consistent capture threshold and sensing amplitude, in contrast to a commercially available alternative. Pacing and continuous telemetric monitoring were achieved in a porcine model. These findings may offer a promising platform for adhesive bioelectronic devices for cardiac monitoring and treatment.

Electro-elution-based purification of covalent DNA-protein cross-links.

Covalent DNA-protein cross-links (DPCs) are pervasive DNA lesions that challenge genome stability and can be induced by metabolic or chemotherapeutic cross-linking agents including reactive aldehydes, topoisomerase poisons and DNMT1 inhibitors. The purification of x-linked proteins (PxP), where DNA-cross-linked proteins are separated from soluble proteins via electro-elution, can be used to identify DPCs. Here we describe a versatile and sensitive strategy for PxP. Mammalian cells are collected following exposure to a DPC-inducing agent, embedded in low-melt agarose plugs and lysed under denaturing conditions. Following lysis, the soluble proteins are extracted from the agarose plug by electro-elution, while genomic DNA and cross-linked proteins are retained in the plug. The cross-linked proteins can then be analyzed by standard analytical techniques such as sodium dodecyl-sulfate-polyacrylamide gel electrophoresis followed by western blotting or fluorescent staining. Alternatively, quantitative mass spectrometry-based proteomics can be used for the unbiased identification of DPCs. The isolation and analysis of DPCs by PxP overcomes the limitations of alternative methods to analyze DPCs that rely on precipitation as the separating principle and can be performed by users trained in molecular or cell biology within 2-3 d. The protocol has been optimized to study DPC induction and repair in mammalian cells but may also be adapted to other sample types including bacteria, yeast and tissue samples.

Synthesis of novel collagen-based aerogel with slit-shaped pore structure: Study on its adsorption mechanism on copper ions

In this study, (SA/BHC)@TE aerogel is successfully prepared based on hydrogen bonding between three components, covalent cross-linking between bovine hide collagen (BHC) and tannin extract (TE), and the gelation of sodium alginate (SA). The adsorption properties of (SA/BHC)@TE on Cu(Ⅱ) are systematically analyzed through a combination of simulations and specific experiments. Firstly, DFT simulations are performed to rapidly predict the possibility of interactions among BHC, SA and TE. Then, experiments are performed to indicate that the (SA/BHC)@TE aerogel is endowed with a core–shell structure, a slit-shaped pore structure, and abundant active centers (–OH, –COOH, –NH2 and –CONH–). (SA/BHC)@TE has a maximum removal efficiency of 90.3 % for Cu(Ⅱ). Consequently, (SA/BHC)@TE successfully achieves selective adsorption of specific ions Cu(Ⅱ) from the mixture with a distribution coefficient of 11.12 L/g. It suggests that the adsorption is mainly multilayer adsorption and chemisorption. Furthermore, the FTIR and XPS studies reveal that the adsorption of Cu(Ⅱ) onto (SA/BHC)@TE is the result of the synergistic effect of coordination, ion exchange and electrostatic interaction. In addition, the (SA/BHC)@TE aerogel is easy to separate and recycle. Therefore, this paper has important implications for the development of selective adsorbents for Cu(Ⅱ) as well as for the resource utilization of collagen.

SYNTHESIS AND STUDY OF THE INFLUENCE OF ALKALI CONCENTRATION AND TEMPERATURE ON THE PHYSICOCHEMICAL PROPERTIES OF CRYOGELS BASED ON GELATIN AND CHITOSAN

Much of the polymer research is focused on improving existing polymers or developing new biomaterials with tunable properties. Natural polymers that have certain segments that contribute to an additional therapeutic effect are more often used as a biocompatible polymer. Polymers can be produced using a variety of methods, including covalent cross-linking, dynamic covalent cross-linking, physical cross-linking, cryopolymerization, 3D printing, electrospinning, etc. Cryopolymerization is a unique method and has several advantages over other methods. By cryofreezing it is possible to obtain a porous structure in which the size and volume of the pores can be controlled by changing the concentration of the initial monomers and temperature. The purpose of this study is to determine the effect of alkali concentration and cryopolymerization temperature on the properties of cryogels. The objects of study in this work are cryogels based on gelatin and chitosan. Methodology. The functional groups of the cryogels were determined by IR spectroscopy. The results of a study of the sorption and desorption of polymers are presented. The results of polymer degradation in phosphate-saline solution over 8 weeks are also shown. These studies were based on changes in mass, that is, they were carried out using the gravimetric method. Conclusion. The results of a study of the influence of alkali concentration and temperature on the physicochemical properties of cryogels based on gelatin and chitosan are presented. Cryogels based on gelatin and chitosan are synthesized without the use of harmful chemical cross-linking agents, which makes them attractive for tissue engineering.

Role of covalent crosslinking and 2D nanomaterials in the fabrication of advanced organic solvent nanofiltration membranes: A review of fabrication strategies, recent advances, and challenges

Organic solvent nanofiltration (OSN) membranes have gained significant attention owing to their pivotal role in various industrial applications, including pharmaceuticals, fine chemicals, and manufacturing. This review provides a comprehensive overview of the recent advances in OSN membrane technology, focusing on membrane materials, fabrication techniques, and strategies for tuning the chemistry, structure, and performance of OSN membranes. Initially, the fundamental principles underlying OSN are described, highlighting the critical parameters influencing membrane selectivity, permeability, and stability in organic solvents. It also focuses on the importance of covalent crosslinking in the design and fabrication of dense polyamide membranes. Subsequently, the design and synthesis of novel membrane materials are discussed, including polymeric, inorganic, and hybrid membranes. The use of 2D nanomaterials is summarized, with an emphasis on their structural characteristics and tailored properties for solvent separation applications. We further explored the innovative fabrication strategies, such as interfacial polymerization, modification of ultrafiltration supports, and tuning of the active layer chemistry by incorporating the membrane structure with porous nanofillers. This review also discusses the inhomogeneity issues between inorganic nanofillers and organic matrices of membranes as well as the strategies to overcome these limitations through proper functionalization. Finally, we identified emerging trends and prospects in OSN membrane research, encompassing sustainability, scalability, and integration with other membrane processes, to address existing challenges and discover new opportunities for efficient solvent separation in diverse industrial sectors.

Designing Conductive Pyrrolidinium‐Based Dual Network Gel Electrolytes: Tailoring Performance with Dynamic and Covalent Crosslinking

AbstractTransitioning toward a carbon‐negative direction necessitates continued development and enhancement of existing lithium battery technologies. A key impediment for these technologies is the utilization of flammable organic solvent‐based electrolytes, which pose significant safety risks. Furthermore, the recyclability of batteries has not reached the level required for transitioning to a circular economy. Here, poly(ionic liquid)‐based dual network gel electrolytes are reported as safer and sustainable alternative materials. The materials employ both, dynamic (up to 45 mol%) and covalent crosslinking (up to 10 mol%), allowing the fabrication of mechanically stable gels with a high content (up to 65 wt%) of ionic liquid/salt both via thermal and photo polymerization. The dual nature of this network in interplay with other key components is systematically investigated. Mechanical stability (up to 0.7 MPa), combined with enhanced ionic conductivity (surpassing 10−4 S cm−1 at room temperature) is achieved via the synergetic combination of dynamic non‐covalent and covalent crosslinking, resulting in improved electrochemical (up to 5 V) and thermal stability (reaching 300 °C) by the embedded ionic liquid. Moreover the presence of the dynamic crosslinks facilitates reprocessing at 70 °C without comrpomising the electrochemical performance, thus reaching full recyclability and reusability.

One stone two birds: Recycling of an agri-waste to synthesize laccase-immobilized hierarchically porous magnetic biochar for efficient degradation of aflatoxin B1 in aqueous solutions and corn oil

Aflatoxin B1 (AFB1) contamination of oils is a serious concern for the safety of edible oil consumers. Enzyme-assisted detoxification of AFB1 is an efficient and safe method for decontaminating oils, but pristine enzymes are unstable in oils and require modifications before use. Therefore, we designed a novel and magnetically separable laccase-carrying biocatalyst containing spent-mushroom-substrate (SMS)-derived biochar (BF). Laccase was immobilized on NH2-activated magnetic biochar (BF-NH2) through covalent crosslinking, which provided physicochemical stability to the immobilized enzyme. After 30 days of storage at 4 °C, the immobilized laccase (product named “BF-NH2-Lac”) retained ~95 % of its initial activity, while after five repeated cycles of ABTS oxidation, ~85 % activity retention was observed. BF-NH2-Lac was investigated for the oxidative degradation of AFB1, which exhibited superior performance compared to free laccase. Among many tested natural compounds as mediators, p-coumaric acid proved the most efficient in activating laccase for AFB1 degradation. BF-NH2-Lac demonstrated >90 % removal of AFB1 within 5.0 h, while the observed degradation efficiency in corn oil and buffer was comparable. An insight into the adsorptive and degradative removal of AFB1 revealed that AFB1 removal was governed mainly by degradation. The coexistence of multi-mycotoxins did not significantly affect the AFB1 degradation capability of BF-NH2-Lac. Investigation of the degradation products revealed the transformation of AFB1 into non-toxic AFQ1, while corn oil quality remained unaffected after BF-NH2-Lac treatment. Hence, this study holds practical importance for the research, knowledge-base and industrial application of newly proposed immobilized enzyme products.

Synthesis of polyethylene-based covalent adaptable networks including 1,2,3-triazolium or imine dynamic cross-links by reactive processing

Polyethylene-based covalent adaptable networks (PE CANs) are obtained by reactive extrusion in a micro-compounder of a commercial maleic anhydride-grafted polyethylene (PE-g-MA) with two tailor-made α,ω-diamine cross-linkers carrying either imine or 1,2,3-triazolium groups as dissociative covalent dynamic bonds. Depending on the chemical nature of the exchangeable bonds, drastically different properties are demonstrated by FTIR, swelling/extractible, reactive dissolution and rheological experiments. The imine-containing PE CAN yields a high gel fraction but rheology and reactive dissolution experiments demonstrate the lack of dynamicity due to side-reactions promoting the formation of non-dynamic covalent cross-links. Such undesirable reaction occurs already during the processing stage from the premature cleavage of the imine bonds into amines, and further formation of permanent imide cross-links by reaction with pendent maleic anhydrides. Conversely, the 1,2,3-triazolium-containing PE CAN presents a lower gel fraction but exhibits viscoelastic properties typical of dissociative CANs. While this material is easily reprocessable by compression moulding, the evolution of the rheological properties at high temperatures (160–200 °C) points toward the occurrence of side reactions slowing down the relaxation dynamics which we attribute to the chemical rearrangement of the 1,2,3-triazolium cross-links. These two examples illustrate the difficulty of using amine-functionalized dynamic cross-links in the synthesis of PE CANs by reactive extrusion using PE-g-MA.

Highly proton-conductive and low swelling polymeric membranes achieved by hydrophilic covalent cross-linking

Proton exchange membranes (PEMs) applied in fuel cell technology suffer from the trade-off between fast proton conduction and durable operation involving dimensional stability, mechanical strength, and oxidative resistance. To address this issue, a novel branched polybenzimidazole (brPBI) was synthesized, covalently cross-linked with (3-chloropropyl)triethoxysilane (CTS), and doped with a novel proton conductor FeATMP to prepare brPBI-CTS/FeATMP membranes. The branching degree of brPBI was optimized to achieve high molecular weight while the branching structure offered high free volume, abundant end-groups, and self-cross-linking moiety that enhanced proton conduction and dimensional/mechanical/oxidative stability. Covalent cross-linking with CTS enhanced the dimensional, mechanical, and oxidative stability while improving the water-assisted proton conduction owing to the hydrophilic nature of siloxane structure formed. At 180 ℃, the proton conductivity of the brPBI3-CTS/FeATMP composite membrane reached 0.136, 0.073, and 0.041 S cm−1 at 100 % RH, 50 % RH, and 0 % RH, respectively, while its swelling ratio after immersion in water at 90 ℃ for 24 h was 4.69 %. The performance of the membranes demonstrated that construction of hydrophilic structure by covalent cross-linking was a successful strategy to break the trade-off effect for PEMs.

Crosslinking of base-modified RNAs by synthetic DYW-KP base editors implicates an enzymatic lysine as the nitrogen donor for U-to-C RNA editing

Sequence-specific cytidine to uridine (C-to-U) and adenosine to inosine editing tools can alter RNA and DNA sequences and utilize a hydrolytic deamination mechanism requiring an active site zinc ion and a glutamate residue. In plant organelles, DYW-PG domain containing enzymes catalyze C-to-U edits through the canonical deamination mechanism. Proteins developed from consensus sequences of the related DYW-KP domain family catalyze what initially appeared to be uridine to cytidine (U-to-C) edits leading to this investigation into the U-to-C editing mechanism. The synthetic DYW-KP enzyme KP6 was found sufficient for C-to-U editing activity stimulated by the addition of carboxylic acids invitro. Despite addition of putative amine/amide donors, U-to-C editing by KP6 could not be observed in vitro. C-to-U editing was found not to be concomitant with U-to-C editing, discounting a pyrimidine transaminase mechanism. RNAs containing base modifications were highly enriched in interphase fractions consistent with covalent crosslinks to KP6, KP2, and KP3 proteins. Mass spectrometry of purified KP2 and KP6 proteins revealed secondary peaks with mass shifts of 319Da. A U-to-C crosslinking mechanism was projected to explain the link between crosslinking, RNA base changes, and the ∼319Da mass. In this model, an enzymatic lysine attacks C4 of uridine to form a Schiff base RNA-protein conjugate. Sequenced RT-PCR products from the fern Ceratopteris richardii indicate U-to-C base edits do not preserve proteinaceous crosslinks in planta. Hydrolysis of a protonated Schiff base conjugate releasing cytidine is hypothesized to explain the completed pathway in plants.

Synergistic effects of covalent crosslinking and hydrophobic association on enhancing thermal and salt resistance of polymeric filtrate reducer

Traditional linear polymeric filtrate reducers for water-based drilling fluids (WBDFs) are insufficient for drilling engineering requirements, even with adjustments in the type and proportion of functional groups in the copolymer, especially under high-temperature and high-salinity conditions. In this study, a dual cross-linked copolymer (named AAS-L4%-M0.5‰) was synthesized through free radical copolymerization using lauryl methacrylate (LMA) as hydrophobic associated segments and N, N’-methylene bisacrylamide (MBA) as the chemical crosslinker. The synergistic effect of covalent micro-crosslinking and hydrophobic association in AAS-L4%-M0.5‰ were systematically investigated and demonstrated. After aging at 220 °C for 16 h, the WBDFs containing 1 % AAS-L4%-M0.5‰ exhibited high-temperature/high-pressure filtration loss (FLHTHP) and American Petroleum Institute filtration loss (FLAPI) of 34 mL and 10 mL, respectively, representing reductions of 50 % and 38 % compared to the linear polymer AAS-L0-M0. Even after aging at 200 °C in saturated salt solution conditions, the WBDFs containing AAS-L4%-M0.5‰ maintain excellent filtration properties with FLAPI value of 7.5 mL, achieving an 83 % reduction compared to AAS-L0-M0. Moreover, because of the three-dimensional spatial network structure formed by dual cross-linking, AAS-L4%-M0.5‰ effectively inhibits unwanted foaming caused by the polyelectrolyte effect. Therefore, this work provides a simple but effective approach to develop temperature-resistant and salt-tolerant filtrate reducers with excellent workability.

Engineering a Hydrazone and Triazole Crosslinked Hydrogel for Extrusion-Based Printing and Cell Delivery.

Covalent adaptable crosslinks, such as the alkyl-hydrazone, endow hydrogels with unique viscoelastic properties applicable to cell delivery and bioink systems. However, the alkyl-hydrazone crosslink lacks stability in biologically relevant environments. Furthermore, when formed with biopolymers such as hyaluronic acid (HA), low molecular weight polymers (<60kDa), or low polymer content (<2 wt%) hydrogels are typically employed as entanglements reduce injectability. Here, a high molecular weight (>60kDa) HA alkyl-hydrazone crosslinked hydrogel is modified with benzaldehyde-poly(ethylene glycol)3-azide to incorporate azide functional groups. By reacting azide-modified HA with a multi-arm poly(ethylene glycol) (PEG) functionalized with bicyclononyne, stabilizing triazole bonds are formed through strain-promoted azide-alkyne cycloaddition (SPAAC). Increasing the fraction of triazole bonds within the hydrogel network from 0% to 12% SPAAC substantially increases stability. The slow gelation kinetics of the SPAAC reaction in the 12% SPAAC hydrogel enables transient self-healing properties and a similar extrusion force as the 0% SPAAC hydrogel. Methyl-PEG4-hydrazide is then introduced to further slowdown network evolution, which temporarily lowers the extrusion force, improves printability, and increases post-extrusion mesenchymal stem cell viability and function in the 12% SPAAC hydrogel. This work demonstrates improved stability and temporal injectability of high molecular weight HA-PEG hydrogels for extrusion-based printing and cell delivery.