Natural polymer-based bioadhesives as hemostatic platforms for wound healing.

Medical adhesives are advanced but challenging alternatives to wound closure and repair, especially in mitigating uncontrolled hemorrhage. Ideal hemostatic adhesives need to meet good biocompatibility and biodegradability, adequate mechanical strength, and strong tissue adhesion functionality under wet and dynamic conditions. Considering these requirements, natural polymers such as polysaccharide, protein and DNA, attract great attention as candidates for making bioadhesives because of their distinctive physicochemical performances and biological properties. This review systematically summarizes the advances of bioadhesives based on natural polysaccharide, protein and DNA. Various physical and chemical cross-linking strategies have been introduced for adhesive synthesis and their hemostatic applications are introduced from the aspect of versatility. Furthermore, the possible challenges and future opportunities of bioadhesives are discussed, providing insights into the development of high-performance hemostatic materials.

One-step fabrication of polylactic acid (PLA) nanofibrous membranes with spider-web-like structure for high-efficiency PM0.3 capture.

High-efficiency air filters are in high demand to protect human health from the threat of ultrafine particulate matters (PM). However, most commercial air filters are less effective for PM0.3 capture and/or still suffer from undesirable pressure drops. They are also typically petroleum-based. Herein, a double-jet synchronous electrospinning technology was demonstrated to fabricate spider-web-like polylactic acid (PLA) nanofibrous membranes (SPNM) in one step. The properties of spinning solutions were regulated to construct favorable multi-scale nanofiber and bead structures that mimicked the structural units in spider-webs. The as-prepared SPNM exhibited excellent filtration efficiency (99.87 %) and high quality factor (0.321 Pa-1) against the PM0.3, while presenting an attractively low pressure drop (19 Pa). Additionally, the filtration performance of SPNM was almost completely preserved during 10-cycle tests and the 6-month long-term tests, showing excellent function stability and durability. Benefiting from its good hydrophobicity (WCA = 143.2°), SPNM also presented a satisfactory filtration efficiency (>99.37 %) with low pressure drop (18 Pa) at an environment with humidity at 90 % against PM0.3. Furthermore, the unique structure increased the mechanical strength of SPNM, facilitating the processability for practical applications. Overall, this work may shed light on a promising approach for developing biomass-based, highly efficient filtration materials with hierarchical structures.

MOF-Embedded Bifunctional Composite Nanofiber Membranes with a Tunable Hierarchical Structure for High-Efficiency PM0.3 Purification and Oil/Water Separation.

Herein, a unique hierarchically structured composite nanofiber membrane, consisting of a zeolitic imidazolate framework-8-embedded polyethersulfone (PES@ZIF8) fiber layer and a polysulfonamide/polyethersulfone (PSA/PES) fiber layer, was successfully developed to cope with the complex environments during the actual filtration/separation process and overcome the conflict between high filtration efficiency and low air pressure resistance. Due to the advantages of the synergistic effect of multicomponents and the bi-layer hierarchical structure, the integrated PES@ZIF8-PSA/PES filter possesses an extremely high air filtration efficiency (up to 99.986%) under a very low pressure drop (only 15 Pa), superior PM0.3 purification capacity (close to 99.95%), long-term recycling ability for purifying real smoke PM2.5 from >800 to <10 µg/m3, extremely high temperature resistance (exceed 200 °C), flame retardancy, good chemical stability, satisfactory transmittance, and robust self-cleaning ability. Apart from these, it achieves effective separation of oil-water mixtures and oil-water emulsions as a result of selective wettability including hydrophobicity and superoleophilicity. In particular, the PES@ZIF8-PSA/PES nanofiber membranes maintain outstanding air filtration and oil/water separation properties under the high temperature or strong acid/alkali conditions. This special comprehensive performance gives the PES@ZIF8-PSA/PES-based filtration/separation membranes a wider application prospect ranging from environmental governance to individual protection and industrial security.

High-Strength and High-Toughness Silk Fibroin Hydrogels: A Strategy Using Dynamic Host-Guest Interactions.

Natural polymer-based hydrogels attract great attention because of their inherent biocompatibility and controllable biodegradability. However, the broad applications of these hydrogels require a combination of high mechanical strength, high toughness, fatigue resistance, as well as self-healing. The integration of this combination into one natural polymer-based hydrogel remains challenging. Here, a molecular design strategy was proposed to fabricate mechanically robust silk fibroin-based hydrogels using host-guest interactions. Silk fibroin molecules was chemically modified with cholesterol (Chol, guest) or ß-cyclodextrin (ß-CD, host), and host-guest interaction between Chol and ß-CD moieties drove the supramolecular assemblies of hydrogels. The dissociation/reassociation behavior of host-guest complexation, serving as sacrificial bonds, endowed hydrogels with effective energy dissipation and rapid self-healing ability. The prepared silk fibroin-based hydrogels exhibited high mechanical strength, high toughness, and remarkable fatigue resistance, superior to conventional silk fibroin hydrogels. Moreover, due to reversible host-guest interactions, hydrogels achieved facile functional recovery after damage without any external stimuli. This design strategy provides an avenue to develop natural polymer-based materials with robust mechanical properties, thus broadening current hydrogel applications.

Fabrication of Silk Fibroin Fluorescent Nanofibers via Electrospinning.

Fluorescent silk fibroin nanofibers were fabricated via electrospinning method with three kinds of fluorescent dyes. Electrospun fluorescent nanofibers showed smooth surfaces and average diameters of 873 ± 135 nm, 835 ± 195 nm, and 925 ± 205 nm, respectively, for silk fibroin-fluorescein sodium, silk fibroin-rhodamine B, and silk fibroin-acridine orange nanofibers containing 2.0 wt% fluorescent dyes. At the same time, the secondary structure of silk fibroin in fluorescent nanofibers was predominantly amorphous conformation without influence by adding different concentrations of fluorescent dyes, as characterized by Fourier transform infrared spectroscopy and X-ray diffraction. Thermal degradation behavior of fluorescent silk fibroin nanofibers with a dramatic decrease in weight residue was observed at around 250 °C. The fluorescence effect of fluorescent silk fibroin nanofibers was changed by changing the concentration of different fluorescent dyes. These fluorescent nanofibers may make promising textile materials for large scale application.

Novel two-step method to form silk fibroin fibrous hydrogel.

Hydrogels prepared by silk fibroin solution have been studied. However, mimicking the nanofibrous structures of extracellular matrix for fabricating biomaterials remains a challenge. Here, a novel two-step method was applied to prepare fibrous hydrogels using regenerated silk fibroin solution containing nanofibrils in a range of tens to hundreds of nanometers. When the gelation process of silk solution occurred, it showed a top-down type gel within 30min. After gelation, silk fibroin fibrous hydrogels exhibited nanofiber network morphology with ß-sheet structure. Moreover, the compressive stress and modulus of fibrous hydrogels were 31.9±2.6 and 2.8±0.8kPa, respectively, which was formed using 2.0wt.% concentration solutions. In addition, fibrous hydrogels supported BMSCs attachment and proliferation over 12days. This study provides important insight in the in vitro processing of silk fibroin into useful new materials.

Silk fibroin/sodium alginate fibrous hydrogels regulated hydroxyapatite crystal growth.

Use of organic templates for controlling the growth of inorganic crystals is one of the research topics in biomimetic field. In particular, oriented growth of hydroxyapatite (HAp) in organic fibrous matrix is provided a new view angle to study biomineralization of bone and its potential biomedical applications. The crystallization of HAp in fibrous hydrogels could mimic such biomineralization. In this paper, we report HAp nanorod crystal synthesized successfully by a biomimetic method using calcium chloride and ammonium dihydrogen phosphate as reagents in the presence of silk fibroin/sodium alginate (SF/SA) fibrous hydrogels. The effects of influence factors such as mineral times, pH, and temperature on controlling HAp nanorod crystals are discussed. The elongated HAp nanorods with rectangular column are grown with the increase of mineral times in biomimetic process. By changing pH, HAp nanorod crystals are obtained at alkaline condition in fibrous hydrogels. Moreover, compared to other temperatures, rod-shaped HAp crystals were formed at 20°C. The results imply this to be an effective method for preparing HAp crystals with controllable morphology for bone repair application.

Influence factors analysis on the formation of silk I structure.

Regenerated silk fibroin aqueous solution was used to study the crystalline structure of Bombyx mori silk fibroin in vitro. By controlling environmental conditions and concentration of silk fibroin solution, it provided a means for the direct preparing silk I structure and understanding the details of silk fibroin molecules interactions in formation process. In this study, silk fibroin molecules were assembled to form random coil at low concentration of solution and then, as the concentration increases, were converted to silk I at 55% relative humidity (RH). At the same time, the structure of silk fibroin forming below 45 °C was mostly in silk I. A partial ternary phase diagram of temperature-humidity-concentration was constructed based on the results. The results showed silk I structure could be controlled by adjusting the external environmental conditions. The enhanced control over silk I structure, as embodied in phase diagram, could potentially be utilized to understand the molecular chain conformation of silk I in further research work.

Novel silk fibroin films prepared by formic acid/hydroxyapatite dissolution method.

Bombyx mori silk fibroin from the silkworm was firstly found to be soluble in formic acid/hydroxyapatite system. The rheological behavior of silk fibroin solution was significantly influenced by HAp contents in dissolved solution. At the same time, silk fibroin nanofibers were observed in dissolved solution with 103.6±20.4nm in diameter. Moreover, the structure behavior of SF films prepared by formic acid/hydroxyapatite dissolution method was examined. The secondary structure of silk fibroin films was attributed to silk II structure (ß-sheet), indicating that the hydroxyapatite contents in dissolved solution were not significantly affected by the structure of silk fibroin. The X-ray diffraction results exhibited obviously hydroxyapatite crystalline nature existing in silk fibroin films; however, when the hydroxyapatite content was 5.0wt.% in dissolved solution, some hydroxyapatite crystals were converted to calcium hydrogen phosphate dehydrate in silk fibroin dissolution process. This result was also confirmed by Fourier transform infrared analysis and DSC measurement. In addition, silk fibroin films prepared by this dissolution method had higher breaking strength and extension at break. Based on these analyses, an understanding of novel SF dissolution method may provide an additional tool for designing and synthesizing advanced materials with more complex structures, which should be helpful in different fields, including biomaterial applications.

Silk dissolution and regeneration at the nanofibril scale.

Native silk features strong, extensible and tough properties which originate from its hierarchical nanofibril structure. In the present study, native silk nanofibrils were obtained by dissolving degummed silk in salt-formic acid (FA), such as CaCl2-FA. The CaCl2-FA dissolved silk by breaking hydrogen bonds in the crystalline region while preserving the nanofibril structures. The dissolution behavior of silk from fibre to nanofibril was determined by Na2CO3 concentration during the degumming process, and was regulated by CaCl2 concentration during the dissolution process. The resulting solution containing silk fibroin (SF) nanofibrils could be easily processed into films with nanofibrous structures and high strength. In addition, high-quality electrospun SF nanofibres could also be generated easily from this solution. The novel dissolution and regeneration behavior of silk at the nanofibril scale provides new insights into methods for the preparation of high-quality silk materials for application in high-tech areas.