Cross-linking Approach Research Articles

Bulk and Interfacial Behavior of Potato Protein-Based Microgels.

This study aims to understand the bulk and interfacial performance of potato protein microgels. Potato protein (PoP) was used to produce microgels of submicrometer diameter via a top-down approach of thermal cross-linking followed by high-shear homogenization of the bulk gel. Bulk "parent" gels were formed at protein concentrations [PoP] = 5-18 wt %, which subsequently varied in their bulk shear elastic modulus (G') by several orders of magnitude (1-100 kPa), G' increasing with increasing [PoP]. The PoP microgels (PoPM) formed from these parent gels had diameters varying between 100 and 300 nm (size increasing with increasing G' and [PoP]), as observed via dynamic light scattering and atomic force microscopy (AFM) of PoPM adsorbed onto silicon. Interfacial rheology (interfacial shear storage and loss moduli, Gi' and Gi″) and interfacial tension (γ) of adsorbed films of PoP (i.e., nonheated PoP) and PoPM (both at tetradecane-water interfaces) were also studied, as well as the bulk rheology of the PoPM dispersions. The results showed that PoPM dispersions (at 50 vol %) had significantly higher bulk viscosity and shear thinning properties compared to the nonmicrogelled PoP at the same overall [PoP], but the bulk rheological behavior was in sharp contrast to the interfacial rheological performance, where Gi' and Gi″ of PoP were higher than for any of the PoPM. This suggests that the deformability and size of the microgels were key in determining the interfacial rheology of the PoPM. These findings may be attributed to the limited capacity for "unfolding" and lateral interactions of the larger PoPM at the interface, which are presumed to be stiffer due to their production from the strongest PoP gels. Our study further confirmed that heating and cooling the adsorbed films of PoPM after their adsorption showed little change, highlighting that hydrogen bonding was limited between the microgel particles.

Jellyfish-Inspired Polyurea Ionogel with Mechanical Robustness, Self-Healing, and Fluorescence Enabled by Hyperbranched Cluster Aggregates.

Ionogels are promising for soft iontronics, with their network structure playing a pivotal role in determining their performance and potential applications. However, simultaneously achieving mechanical toughness, low hysteresis, self-healing, and fluorescence using existing network structures is challenging. Drawing inspiration from jellyfish, we propose a novel hierarchical crosslinking network structure design for in situ formation of hyperbranched cluster aggregates (HCA) to fabricate polyurea ionogels to overcome these challenges. Leveraging the disparate reactivity of isocyanate groups, we induce the in situ formation of HCA through competing reactions, enhancing toughness and imparting the clustering-triggered emission of ionogel. This synergy between supramolecular interactions in the network and plasticizing effect in ionic liquid leads to reduced hysteresis of the ionogel. Furthermore, the incorporation of NCO-terminated prepolymer with dynamic oxime-urethane bonds (NPU) enables self-healing and enhances stretchability. Our investigations highlight the significant influence of HCA on ionogel performance, showcasing mechanical robustness including high strength (3.5 MPa), exceptional toughness (5.5 MJ m-3), resistance to puncture, and low hysteresis, self-healing, as well as fluorescence, surpassing conventional dynamic crosslinking approaches. This network design strategy is versatile and can meet the various demands of flexible electronics applications.

Enhancement of CO2 hydrogenation to formate using formate dehydrogenase immobilized on UiO66 and its derivatives

In the present work, a highly stable zirconium-based metal-organic framework (MOF), UiO66, and its derivative, UiO66-NH2, were tested as support materials to immobilize Formate dehydrogenase (FDH) for use in CO2 hydrogenation. Both physical adsorption and cross-linking approaches were tested for immobilization. Cross-linking with glutaraldehyde has been suggested to enhance the stability of the enzyme and reduce leaching, which is prone to physical attachment. The adsorption isotherm and kinetics were best described by Sips and pseudo-second-order models, respectively. The influences of the secondary structure of the protein on catalytic performance and formate production were studied. Immobilization of FDH resulted in a change in the secondary structure, with the α-helical content increased from 29.4% of the free enzyme to 43% after immobilization on UiO66 and 100% after immobilization on UiO66-NH2. This structural change significantly enhanced the enzyme activity. At optimum conditions of pH 5.5 and 30 mM NaHCO3, the activity of immobilized FDH was 19.6 times higher than that of free FDH. Formate production was also enhanced using immobilized FDH on UiO66-NH2, where production was 2.4 times higher than that achieved using free FDH. Better stability and reusability were achieved by cross-linking with glutaraldehyde. The results of this work provide a novel insight into the changes in the secondary structure of FDH after immobilization and its positive effect on catalytic efficiency. These findings are expected to pave the way for the commercial applications of FDH for CO2 utilization

Antibacterial and antioxidative hydrogel dressings based on tannic acid-gelatin/oxidized sodium alginate loaded with zinc oxide nanoparticles for promoting wound healing

Wound infection resulting in delayed wound healing and wound deterioration remains a clinical challenge. Recently, multifunctional hydrogel dressing was a promising strategy which has attracted wide attention in preventing wound infection and promoting wound healing. In this study, a hybrid hydrogel made of gelatin (GL), tannic acid (TA), oxidized sodium alginate (OSA), and zinc oxide nanoparticles (ZnO NPs) was prepared mainly by double network cross-linking approach, named tannic acid-gelatin/oxidized sodium alginate/zinc oxide (TA-GL/OSA/ZnO). The composite hydrogels exhibited improved mechanical properties, which provided by TA modified the structure of GL network, Schiff base reaction between GL and OSA, and the strengthening effect of ZnO NPs. Meanwhile, the composite hydrogel showed high antibacterial activity against Staphylococcus aureus (S. aureus) (97.8 % ± 0.9 %) and Escherichia coli (E. coli) (96.6 % ± 1.2 %), attributed to the synergistic effect of TA and ZnO NPs. Furthermore, benefiting from the good antioxidative properties of TA, the sustain-released Zn2+ with the good capability to kill bacteria, and promoting the regeneration of skin epithelial tissues in BALB/c mice constantly, the multifunctional hydrogel had a significant therapeutic effect on wound healing and broad application prospects.

Antibiotic-eluting scaffolds with responsive dual-release kinetics facilitate bone healing and eliminate S. aureus infection

Osteomyelitis (OM) is a progressive, inflammatory infection of bone caused predominately by Staphylococcus aureus. Herein, we engineered an antibiotic-eluting collagen-hydroxyapatite scaffold capable of eliminating infection and facilitating bone healing. An iterative freeze-drying and chemical crosslinking approach was leveraged to modify antibiotic release kinetics, resulting in a layered dual-release system whereby an initial rapid release of antibiotic to clear infection was followed by a sustained controlled release to prevent reoccurrence of infection. We observed that the presence of microbial collagenase accelerated antibiotic release from the crosslinked layer of the scaffold, indicating that the material is responsive to microbial activity. As exemplar drugs, vancomycin and gentamicin-eluting scaffolds were demonstrated to be bactericidal, and supported osteogenesis in vitro. In a pilot murine model of OM, vancomycin-eluting scaffolds were observed to reduce S. aureus infection within the tibia. Finally, in a rabbit model of chronic OM, gentamicin-eluting scaffolds both facilitated radial bone defect healing and eliminated S. aureus infection. These results show that antibiotic-eluting collagen-hydroxyapatite scaffolds are a one-stage therapy for OM, which when implanted into infected bone defects simultaneously eradicate infection and facilitate bone tissue healing.

Jellyfish‐Inspired Polyurea Ionogel with Mechanical Robustness, Self‐Healing, and Fluorescence Enabled by Hyperbranched Cluster Aggregates

AbstractIonogels are promising for soft iontronics, with their network structure playing a pivotal role in determining their performance and potential applications. However, simultaneously achieving mechanical toughness, low hysteresis, self‐healing, and fluorescence using existing network structures is challenging. Drawing inspiration from jellyfish, we propose a novel hierarchical crosslinking network structure design for in situ formation of hyperbranched cluster aggregates (HCA) to fabricate polyurea ionogels to overcome these challenges. Leveraging the disparate reactivity of isocyanate groups, we induce the in situ formation of HCA through competing reactions, enhancing toughness and imparting the clustering‐triggered emission of ionogel. This synergy between supramolecular interactions in the network and plasticizing effect in ionic liquid leads to reduced hysteresis of the ionogel. Furthermore, the incorporation of NCO‐terminated prepolymer with dynamic oxime–urethane bonds (NPU) enables self‐healing and enhances stretchability. Our investigations highlight the significant influence of HCA on ionogel performance, showcasing mechanical robustness including high strength (3.5 MPa), exceptional toughness (5.5 MJ m−3), resistance to puncture, and low hysteresis, self‐healing, as well as fluorescence, surpassing conventional dynamic crosslinking approaches. This network design strategy is versatile and can meet the various demands of flexible electronics applications.

Effects of quaternization sites and crossing methods on the slow-release and antibacterial effects of hydroxypropyltrimethyl ammonium chloride chitosan/dialdehyde chitosan-based film

In this study, the active food packaging film were prepared using hydroxypropyltrimethyl ammonium chloride chitosan with different substitution sites (O-HACC & N-HACC) and dialdehyde chitosan (DCS) grafted with protocatechuic acid (PA). To explore the effect of chitosan quaternization positions and crosslinking approaches on the slow-release and antibacterial properties, the double-crosslinked film were fabricated through the self-coupling reaction of PA and Schiff base reaction between amino groups on HACC and aldehyde groups on DCS. The HACC/DCS-based film exhibited stable porous three-dimensional networks with high nisin loading ratios (>90 %). With the participation of the catechol-catechol structure, the dense double-crosslinked film effectively restricted the diffusion of the water molecules, resulting in excellent slow-release properties fitting with the Korsmeyer-Peppas kinetic model. Especially, O-HACC/PA-g-DCS film, which had more reaction sites for Schiff base crosslinking than N-HACC, exhibited the equilibrium swelling ratio of 800 % at 60 h and could sustainably release nisin via non-Fickian diffusion behavior until 48 h. Moreover, the HACC/DCS-based double-crosslinked film performed good long-time antibacterial activity and preservation effects on salmon. On the 10th day of storage, the TVBN of N-HACC/PA-g-DCS and O-HACC/PA-g-DCS groups were only 28.26 ± 1.93 and 29.06 ± 1.68 mg/100 g and still lower than the thresholds.

Porous calcium silicate bioactive material-alginate composite for bone regeneration.

Bone tissue engineering aims to address bone-related problems that arise from trauma, infection, tumors, and surgery. Polymer and calcium silicate bioactive material (BM) based composites are commonly preferred as potential materials for bone treatment. However, the polymer has low bioactivity, thus, the current work aims to prepare a composite scaffold based on BM-sodium alginate (Alg) by varying the Alg percentage to optimize the porous nature of the composite. Primarily, the BM was synthesized by a simple precipitation method using rice husk and eggshell as the precursors of silica and calcium, while the BM-Alg composite was prepared by a facile cross-linking approach. The BM-Alg composite was studied using XRD, FTIR, SEM, and BET techniques. Further, an in vitro bioactivity study was performed in simulated body fluid (SBF) which shows hydroxyapatite formation. The in vitro haemolysis study displayed less than 5% haemolysis. Subsequently, the angiogenesis study was carried out using the ex ovo CAM model which reveals enhanced neovascularization. The MG-63 cells were used to study the biocompatibility, and they displayed a non-toxic nature at a concentration of 10 mg mL-1. Further, the in vivo biocompatibility results also reveal its non-toxic nature. Thus, the BM-Alg composite acts as a potential biocompatible material for bone tissue engineering applications.

A thermal cross-linking approach to developing a reinforced elastic chitosan cryogel for hemostatic management of heavy bleeding

Uncontrolled hemorrhage stands as the primary cause of potentially preventable deaths following traumatic injuries in both civilian and military populations. Addressing this critical medical need requires the development of a hemostatic material with rapid hemostatic performance and biosafety. This work describes the engineering of a chitosan-based cryogel construct using thermo-assisted cross-linking with α-ketoglutaric acid after freeze-drying. The resulting cryogel exhibited a highly interconnected macro-porous structure with low thermal conductivity, exceptional mechanical properties, and great fluid absorption capacity. Notably, assessments using rabbit whole blood in vitro, as well as rat liver volume defect and femoral artery injury models simulating severe bleeding, showed the remarkable hemostatic performance of the chitosan cryogel. Among the cryogel variants with different chitosan molecular weights, the 150 kDa one demonstrated superior hemostatic efficacy, reducing blood loss and hemostasis time by approximately 73 % and 63 % in the hepatic model, and by around 60 % and 68 %, in the femoral artery model. Additionally, comprehensive in vitro and in vivo evaluations underscored the good biocompatibility of the chitosan cryogel. Taken together, these results strongly indicate that the designed chitosan cryogel configuration holds significant potential as a safe and rapid hemostatic material for managing severe hemorrhage.

Glucose detection: In-situ colorimetric analysis with double-layer hydrogel microneedle patch based on polyvinyl alcohol and carboxymethyl chitosan

Skin interstitial fluid (ISF) has emerged as a significant reservoir of biomarkers for disease diagnosis and prevention. Microneedle (MN) patches are regarded as an optimal platform for ISF extraction from the skin due to their non-invasive nature. However, challenges such as prolonged sampling durations and complex detection procedures impede timely metabolic analysis. In this investigation, we amalgamated MN technology with immobilized enzyme technology to fabricate a dual-layer MN patch integrating sampling and detection functionalities, thereby enabling in-situ colorimetric detection of hyperglycemia. The tip layer of the patch, comprising polyvinyl alcohol/carboxymethyl chitosan (PVA/CMCS) MN, was synthesized utilizing a chemical crosslinking approach for the first time, with glucose oxidase (GOx) being incorporated. The hydrophilicity of CMCS expedited the extraction process, facilitating the retrieval of approximately 10 mg of ISF within 10 min. The backing layer consisted of an immobilized polyvinyl alcohol-chitosan-horseradish peroxidase (PVA-CS-HRP) hydrogel film loaded with 3,3′, 5,5′-tetramethylbenzidine (TMB). Incorporating macromolecular polymer PVA and CS for HRP immobilization addressed the issue of poor stability associated with traditional natural enzymes, thereby enhancing the sensitivity of the reaction system. The in-situ colorimetric sensor facilitated minimally invasive ISF extraction and swift conversion of glucose levels into detectable color changes.

A highly durable and biocompatible bionic collagen implant with exceptional anti-calcification and collagen regeneration capabilities for improved skin rejuvenation

Skin aging, a complex and inevitable biological process, considerably impacts an individual’s physical appearance and overall well-being. While collagen-based implants hold potential for skin rejuvenation, their clinical application is limited by the poor durability of non-crosslinked implants and the negative impacts of crosslinking agents, such as cytotoxicity and calcification. Herein, we report a highly durable and biocompatible bionic collagen implant for superior skin rejuvenation with advanced anti-calcification characteristics and enhanced collagen regeneration. Utilizing biomimetic self-assembly and covalent crosslinking approach, we successfully created long-lasting and biomimetic collagen implants with densely-packed collagen fibers. Crosslinking of collagen fibers with a low concentration of N-hydroxysuccinimide activated suberic acid (NHS-SA) was highly efficient, resulting in complete crosslinking and thicker collagen fiber formation with a uniform network structure. Compared with glutaraldehyde-crosslinked collagen fibers, NHS-SA-crosslinked assembled collagen fibers (NACF) demonstrated considerably improved thermal stability and durability. Furthermore, the NACF implant exhibited superior biocompatibility, establishing NHS-SA crosslinked collagen fibers as a safer and more bioactive choice for implant applications. In mouse subcutaneous implant models, the NACF implant outperformed other collagen implants, demonstrating exceptional biocompatibility, effective collagen regeneration, and excellent anti-calcification potential. The NACF implant shows immense promise in collagen regeneration, offering considerable potential to advance skin rejuvenation therapies.

Empowering PLA Bioplastics: Elevating applications horizon through groundbreaking Eco-Innovative Fibrillation, chain Extension, and crosslinking techniques

This comprehensive study introduces pioneering techniques in the toughening of polylactic acid (PLA) by incorporating thermoplastic polyurethane (TPU) nanofibrils, leveraging two distinct crosslinking methods to significantly enhance the material’s mechanical performance. Method 1 employs a silane/moisture crosslinking process, whereas Method 2 utilizes a tailored diisocyanate crosslinking approach, offering a more environmentally sustainable alternative. Molecular structural analysis was performed extensively by using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H NMR), gel permeation chromatography (GPC), rheological assessments, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). Method 2 not only preserves TPU nanofibrils but also elevates the mechanical properties of PLA-TPU composites beyond the capabilities of Method 1. Notably, by leveraging the simultaneous crosslinking of TPU and chain extension of PLA with the tailored diisocyanate approach, we enhance PLA’s mechanical properties and energy absorption capabilities. These advancements are achieved without a high rubber content, which typically compromises strength/stiffness, thermomechanical stability, crystallization, and transparency of PLA. The resulting composites prepared via Method 2 display remarkable increases in tensile toughness, ranging from 30-60 MPa, and impact strength, achieving a span of 60–140 J/m. This is primarily due to the occurrence of a brittle-to-ductile transition (BDT) at only 3 wt% nanofibril TPU content while maintaining a high PLA modulus of 3 GPa. This critical balance between chain-extending and crosslinking reactions ensures the maintenance of PLA’s inherent strength/stiffness, crystallization, and optical clarity. The research presented here marks a significant shift in the development of tougher, more thermally stable, transparent, and sustainable polymer blends and composites. Method 2, with its tailored fiber size reduction (90–280 nm), and environmental consciousness, broadens the horizon of PLA’s applications.

Applications of Functional Polymeric Eutectogels.

Over the past two decades, deep eutectic solvents (DESs) have captured significant attention as an emergent class of solvents that have unique properties and applications in differing fields of chemistry. One area where DES systems find utility is the design of polymeric gels, often referred to as "eutectogels," which can be prepared either using a DES to replace a traditional solvent, or where monomers form part of the DES themselves. Due to the extensive network of intramolecular interactions (e.g., hydrogen bonding) and ionic species that exist in DES systems, polymeric eutectogels often possess appealing material properties-high adhesive strength, tuneable viscosity, rapid polymerization kinetics, good conductivity, as well as high strength and flexibility. In addition, non-covalent crosslinking approaches are possible due to the inherent interactions that exist in these materials. This review considers several key applications of polymeric eutectogels, including organic electronics, wearable sensor technologies, 3D printing resins, adhesives, and a range of various biomedical applications. The design, synthesis, and properties of these eutectogels are discussed, in addition to the advantages of this synthetic approach in comparison to traditional gel design. Perspectives on the future directions of this field are also highlighted.

Adhesive Antibacterial Moisturizing Nanostructured Skin Patch for Sustainable Development of Atopic Dermatitis Treatment in Humans.

Atopic dermatitis (AD) is a chronic inflammatory skin disease with a complex etiology that lacks effective treatment. The therapeutic goals include alleviating symptoms, such as moisturizing and applying antibacterial and anti-inflammatory medications. Hence, there is an urgent need to develop a patch that effectively alleviates most of the AD symptoms. In this study, we employed a "green" cross-linking approach of poly(vinyl alcohol) (PVA) using glycerol, and we combined it with polyacrylonitrile (PAN) to fabricate core-shell (CS) nanofibers through electrospinning. Our designed structure offers multiple benefits as the core ensures controlled drug release and increases the strength of the patch, while the shell provides skin moisturization and exudate absorption. The efficient PVA cross-linking method facilitates the inclusion of sensitive molecules such as fermented oils. In vitro studies demonstrate the patches' exceptional biocompatibility and efficacy in minimizing cell ingrowth into the CS structure containing argan oil, a property highly desirable for easy removal of the patch. Histological examinations conducted on an ex vivo model showed the nonirritant properties of developed patches. Furthermore, the eradication of Staphylococcus aureus bacteria confirms the potential use of CS nanofibers loaded with argan oil or norfloxacin, separately, as an antibacterial patch for infected AD wounds. In vivo patch application studies on patients, including one with AD, demonstrated ideal patches' moisturizing effect. This innovative approach shows significant promise in enhancing life quality for AD sufferers by improving skin hydration and avoiding infections.

Cross-Linked Cellulose Nanocrystal Membranes with Cholesteric Assembly.

Forming membranes by tangential flow deposition of cellulose nanocrystal (CNC) suspensions is an attractive new approach to bottom-up membrane fabrication, providing control of separation performance using shear rate and ionic strength. Previously, the stabilization of these membranes was achieved by irreversibly coagulating the deposited layer upon the permeation of a high-ionic-strength salt solution. Here, we demonstrate for the first time the chemical cross-linking of carboxyl-containing TEMPO-oxidized CNCs by Ag(I)-catalyzed oxidative decarboxylation and the stabilization of CNC membranes using this post-treatment. Cross-linking of TEMPO-CNCs was first demonstrated in suspension via turbidity, dynamic light scattering, and storage (G') and loss (G″) moduli measurements. Membranes were formed by filtering a 0.15 wt % TEMPO-CNC suspension onto a porous support, followed by permeation of the cross-linking solution containing AgNO3 and KPS through the deposited layer. Rejection for Blue Dextran with a 5 kDa molecular weight was 95.3 ± 1.9%, 90.6 ± 3.7%, and 95.9 ± 1.0% for membranes made from suspensions of TEMPO-CNC, desulfated TEMPO-CNC. and TEMPO-CNC with 100 mM NaCl, respectively. Suspensions with added NaCl led to membranes with improved stability and cholesteric self-assembly in the membrane layer. Membranes subjected to cross-linking post-treatment remained intact upon drying, while those stabilized physically using 200 mM AlCl3 solution were cracked, demonstrating the advantage of the cross-linking approach for scale-up, which requires drying of the membranes for module preparation and storage.

Ready-to-print alginate inks: The effect of different divalent cations on physico-chemical properties of 3D printable alginate hydrogels

Studies about the use of different divalent cations to produce 3D printed scaffolds are almost limited to their application as secondary crosslinking agents after the printing of alginate. For this reason, this research aims to demonstrate the possibility to develop alginate hydrogel-inks for 3D-printing application, exploiting the ionotropic gelation in a preprint step, by paying attention to the role of divalent cations on hydrogel-inks properties. The investigation of transversal relaxation time highlighted differences among inks (barium-ink 90.04 ms, calcium-ink 84.33 ms, and zinc-ink 75.05 ms) suggesting a potential influence of different cations. If all the inks showed a shear thinning behaviour with similar flowability index (0.153±0.018), they were characterised by different consistency index (from 2420 to 574 Pa•s), extrudability and homogeneity, parameters that influence the printing setup. In fact, to reach the same flowability and thus low deviation in the layer width for all inks, a variation in printing pressure and speed was necessary. Overall, it can be deduced that alginate inks preparation following a preprint crosslinking approach could be a valid method to overcome the alginate printability issues underlining the possibility to select the crosslinking cation according to the technological properties wanted for the final matrix.

Tailored design of NHS–SS–NHS cross-linked chitosan nano-hydrogels for enhanced anti-tumor efficacy by GSH-responsive drug release

The traditional chemotherapeutic agents’ disadvantages such as high toxicity, untargeting and poor water solubility lead to disappointing chemotherapy effects, which restricts its clinical application. In this work, novel size-appropriate and glutathione (GSH)-responsive nano-hydrogels were successfully prepared via the active ester method between chitosan (containing –NH2) and cross-linker (containing NHS). Especially, the cross-linker was elaborately designed to possess a disulfide linkage (SS) as well as two terminal NHS groups, namely NHS–SS–NHS. These functionalities endowed chitosan-based cross-linked scaffolds with capabilities for drug loading and delivery, as well as a GSH-responsive mechanism for drug release. The prepared nano-hydrogels demonstrated excellent performance applicable morphology, excellent drug loading efficiency (∼22.5%), suitable size (∼100 nm) and long-term stability. The prepared nano-hydrogels released over 80% doxorubicin (DOX) after incubation in 10 mM GSH while a minimal DOX release less than 25% was tested in normal physiological buffer (pH = 7.4). The unloaded nano-hydrogels did not show any apparent cytotoxicity to A 549 cells. In contrast, DOX-loaded nano-hydrogels exhibited marked anti-tumor activity against A 549 cells, especially in high GSH environment. Finally, through fluorescent imaging and flow cytometry analysis, fluorescein isothiocyanate-labeled nano-hydrogels show obvious specific binding to the GSH high-expressing A549 cells and nonspecific binding to the GSH low-expressing A549 cells. Therefore, with this cross-linking approach, our present finding suggests that cross-linked chitosan nano-hydrogel drug carrier improves the anti-tumor effect of the A 549 cells and may serve as a potential injectable delivery carrier.

Polyurethane dispersion/carboxylated nitrile butadiene rubber blends produced by a greener dual crosslinking approach

A latex blend comprising polyurethane dispersion (PUD) and carboxylated nitrile butadiene rubber (XNBR) in an 80:20 ratio was prepared in the presence of epoxide and organo-modified siloxane crosslinkers. The aim of the study was to enhance the tensile, thermal, and chemical properties of the PUD/XNBR latex blend without the incorporation of sulphur and accelerator. Studies revealed that the combined action of epoxide and organo-modified siloxane crosslinker demonstrated adequate intermolecular hydrogen bonding, thereby resulting in superior tensile strength. Differential scanning calorimetry (DSC) analysis showed alterations in chain orientation and melting enthalpy due to the introduction of two crosslinkers that impart ordered hydrogen bonding to a certain degree. The compactness of the structure of the cure molecule may be closely related to the heating enthalpy, as in the following sequence, PUD80/XNBR20/E1 will have a loosely packed structure, followed by PUD80/XNBR20/E0.5S0.5 and PUD80/XNBR20/S1. Chemical swelling studies revealed the impact of crosslinker combinations on hydrogen bonding (both ordered and disordered), affirming the consequential enhancement in chemical resistance. This study confirms that the attained intermolecular hydrogen bonding results in desirable mechanical and chemical resistance performance, making the latex blend suitable for glove applications.

DEVELOPING NEXT-GENERATION INJECTABLE ADIPOSE TISSUE GRAFTS FOR SOFT-TISSUE RECONSTRUCTION

IntroductionAutologous fat grafting has favourable potential as a regenerative strategy and is the current gold-standard to repair large contour defects, as needed in breast reconstruction after mastectomy and traumatic soft tissue reconstruction. Clinically, there is a limit on the volume of lipoaspirate which can be utilised to repair a soft-tissue defect. Surgical complications are the result of poor structural fidelity of lipoaspirate and graft resorption as a filling material and are hindered further by poor graft vascularisation. This study aims to develop injectable lipoaspirate-derived adipose tissue grafts with enhanced biologically and clinically-admissible structural and functional properties adopting light photocrosslinking of unmodified lipoaspirate.MethodsPatient-derived lipoaspirate was harvested and crosslinked using novel photoinitiator and exposure to visible light (wavelength 450nm) in surgery, establishing bonds between extracellular matrix (ECM) proteins within the material. The degree of crosslinking was tuned (photoinitiator concentration, light exposure, light intensity) and covalent bond formation measured using mass spectrometry. To predict patient response, SWATH-MS was used to identify differences in patient ECM and crosslinked grafts were implanted in vivo using a subcutaneous mouse model. Functional vessel formation and resorption were quantified using micro-CT and tissue-remodelling was assessed via histology.ResultsThere was an increase in the relative abundance of covalent bonds present with increasing degree of crosslinking. When injected, crosslinked lipoaspirate had better shape fidelity compared with native lipoaspirate – demonstrated by a smaller fibre diameter. Crosslinked lipoaspirate remained viable over long term culture and resulted in more predictable resorption profiles when implanted in vivo.ConclusionsThe crosslinking approach described here is tunable and functional across different patient samples. Improving the structural properties of lipoaspirate through minimal manipulation has clinical utility for the delivery of grafts with higher shape fidelity and therefore increased graft survival when implanted.

Functionalizing DNA Origami by Triplex-Directed Site-Specific Photo-Cross-Linking.

Here, we present a cross-linking approach to covalently functionalize and stabilize DNA origami structures in a one-pot reaction. Our strategy involves adding nucleotide sequences to adjacent staple strands, so that, upon assembly of the origami structure, the extensions form short hairpin duplexes targetable by psoralen-labeled triplex-forming oligonucleotides bearing other functional groups (pso-TFOs). Subsequent irradiation with UVA light generates psoralen adducts with one or both hairpin staples leading to site-specific attachment of the pso-TFO (and attached group) to the origami with ca. 80% efficiency. Bis-adduct formation between strands in proximal hairpins further tethers the TFO to the structure and generates "superstaples" that improve the structural integrity of the functionalized complex. We show that directing cross-linking to regions outside of the origami core dramatically reduces sensitivity of the structures to thermal denaturation and disassembly by T7 RNA polymerase. We also show that the underlying duplex regions of the origami core are digested by DNase I and thus remain accessible to read-out by DNA-binding proteins. Our strategy is scalable and cost-effective, as it works with existing DNA origami structures, does not require scaffold redesign, and can be achieved with just one psoralen-modified oligonucleotide.