Pullulan Hydrogel Research Articles

Carboxymethyl chitosan/dialdehyde quaternized pullulan self-healing hydrogel loaded with tranexamic acid for rapid hemostasis

In this study, we designed novel self-healing hydrogels (CMC/DAQP-HGs) using carboxymethyl chitosan (CMC) and dialdehyde quaternized pullulan (DAQP), aimed at loading tranexamic acid (TA) for rapid hemostasis. Meanwhile, CMC/dialdehyde pullulan (DAP) hydrogels (CMC/DAP-HGs) were prepared for comparison with CMC/DAQP-HGs. Experimental results showed that (1) DAQP, DAP, CMC/DAQP-HGs, and CMC/DAP-HGs were successfully prepared; (2) both types of hydrogels demonstrated excellent swelling (swelling ratio of 12.66–22.18 g/g), water retention (> 24 h), self-healing, and injectable properties, biocompatibility (hemolysis ratio < 2 %, relative cell viability of L929 and HSF > 80 %), and degradability; (3) CMC/DAQP-HGs had superior adhesive, antibacterial, and hemostatic properties compared to CMC/DAP-HGs, with CMC/DAQP-HG1 showing the best performance, including a tissue adhesion strength of 6.54 kPa, ~100 % of inhibition against E. coli and S. aureus, and hemostasis time in the three animal models <312 s; (4) the novel hydrogels effectively encapsulated tranexamic acid (TA) and controlled TA release; and (5) the addition of TA significantly enhanced the hydrogels' hemostatic efficacy, with the hemostasis time values in the TA-loaded CMC/DAQP-HG1 (TA/CMC/DAQP-HG1) group being reduced by >56 % compared to those in the gelatin sponge group, indicating that TA/CMC/DAQP-HG1 had the potential to be an ideal hemostatic dressing.

Facile synthesis of ATTM@ZIF-8 modified pullulan hydrogels for enhanced adsorption of Congo red and malachite green

Efficient capture of dyes from wastewater is of great importance for environmental remediation. Yet constructing adsorbents with satisfactory adsorption efficiency and low cost remains a major challenge. This work reports a simple and scalable method for the fabrication of functionalized porous pullulan hydrogel adsorbent decorated with ATTM@ZIF-8 for the adsorption of congo red (CR) and malachite green (MG). The embedding of ammonium tetrathiomolybdate (ATTM) into the ZIF-8 nanoclusters offered additional adsorption sites and enlarged the pore size of the resulting ATTM@ZIF-8. The homogeneous dispersion of the nanoparticles in the three-dimensional network of polysaccharide gels prevents their agglomeration and thus improves the affinity for dye molecules. The resulting adsorbent AZP-20 at optimized composite ratios exhibits high activity, selectivity, interference resistance, reusability and cytocompatibility in dye adsorption applications, and possesses high removal rate of dye in real water systems. Batch experiments demonstrated that the adsorption rate of AZP-20 for MG and CR was 1645.28 mg g−1 and 680.33 mg g−1, and would be influenced by pH conditions. Adsorption kinetics followed pseudo-second-order model. Adsorption isotherms followed Langmuir model for MG and Freundlich model for CR. The adsorption of dye molecules primarily relied on electrostatic interaction (MG) and π-π stacking interaction (CR). Conclusively, the prepared AZPs adsorbent illuminated good application prospects in the treatment of complex component dye wastewater.

Developing and analyzing photo-crosslinkable cinnamoyl-modified pullulan hydrogels for drug delivery applications

A hydrogel created by modifying pullulan with cinnamoyl groups (Pul-CM) through an esterification process was developed as an effective vehicle for delivering the well-known drug model, caffeine. Initially, pullulan biopolymer was expanded, followed by the addition of cinnamoyl groups using cinnamoyl chloride. These modifications were confirmed through various spectroscopic and instrumental techniques, verifying their proposed chemical structures. The newly created Pul-CM hydrogel demonstrated the ability to crosslink without initiators when exposed to UV light for sufficient durations. This crosslinking is attributed to the creation of cyclobutane rings that link the pullulan chains via a [2π+2π] cyclization process facilitated by the cinnamoyl groups' –CH=CH– bonds. The progress of Pul-CM crosslinking was tracked by the reduction in the UV spectral peak associated with the cinnamate groups, followed by an examination of the gel's efficiency and its swelling behavior under UV light. Furthermore, these hydrogel derivatives show significant promise as drug delivery systems, offering adjustable drug release rates by altering the hydrogel's crosslinking level through either cinnamoyl modification or the duration of UV light exposure.

Chitosan-Oxidized Pullulan Hydrogels Loaded with Essential Clove Oil: Synthesis, Characterization, Antioxidant and Antimicrobial Properties.

Emulsion hydrogels are promising materials for encapsulating and stabilizing high amounts of hydrophobic essential oils in hydrophilic matrices. In this work, clove oil-loaded hydrogels (CS/OP-C) are synthesized by combining covalent and physical cross-linking approaches. First, clove oil (CO) was emulsified and stabilized in a chitosan (CS) solution, which was further hardened by Schiff base covalent cross-linking with oxidized pullulan (OP). Second, the hydrogels were subjected to freeze-thaw cycles and, as a result, the clove oil was stabilized in physically cross-linked polymeric walls. Moreover, due to cryogelation, the obtained hydrogels exhibited sponge-like porous interconnected morphology (160-250 µm). By varying the clove oil content in the starting emulsion and the degree of cross-linking, the hydrogels displayed a high water retention capacity (swelling ratios between 1300 and 2000%), excellent elastic properties with fast shape recovery (20 s) after 70% compression, and controlled in vitro clove oil release in simulated skin conditions for 360 h. Furthermore, the prepared clove oil-loaded hydrogels had a strong scavenging activity of 83% and antibacterial and antifungal properties, showing a bacteriostatic effect after 48 and 72 h against S. aureus and E. coli. Our results recommend the new clove oil-embedded emulsion hydrogels as promising future materials for application as wound dressings.

Influence of Crosslinker on Pullulan Hydrogel for Iontophoresis Controlled Transdermal Aspirin Release

Influence of Crosslinker on Pullulan Hydrogel for Iontophoresis Controlled Transdermal Aspirin Release

Using embossing ice particulate method to prepare polyvinyl alcohol/pullulan hydrogels with surface open pores loaded with microspheres for breast cancer treatment

In the post-operative treatment of breast cancer, early prevention of locoregional recurrence is crucial to avoid metastasis of cells from leftover microtumor tissues. The limitations in conventional drug delivery systems show a growing clinical demand for disease-specific drug-releasing systems. This study explores a novel poly(vinyl alcohol)/pullulan (PVA/PUL) hydrogel system for local drug delivery in post-operative breast cancer treatment. Hydrogel was produced by combination of lyophilization and embossing ice particulate techniques to create microspheres loaded open pores on the hydrogel surface for localized release of doxorubicin-loaded polycaprolactone microspheres (DOX-PCL-MSs). PVA/PUL hydrogel was successfully crosslinked with glutaraldehyde and stabilized hydrogel structure has possessed slow degradation rate and increasing water retention through 12 days. Release of DOX after 7 and 16 days from DOX-PCL-MSs loaded hydrogels were slower with a 6.2 ± 8.9 % and 56.6 ± 4.5 % release compared to 60.9 ± 14.6 % and 76.8 ± 19.7 % release from free DOX loaded hydrogel since DOX release was controlled by PCL microspheres. When interacted with human breast cancer cell line (MCF-7), DOX-PCL-MSs were able to disrupt cell and spheroid morphology after 7 days at concentrations as low as 12 μg/mL loaded DOX. In vitro cytotoxicity study has showed that, DOX-PCL-MSs loaded hydrogel was able to decrease MCF-7 viability after 7 days of incubation with controlled release of DOX. While free DOX releasing hydrogel has lost cytotoxic activity even after 4 days of incubation. Furthermore, ability of PVA/PUL hydrogel to support L929 cell attachment was shown in the study, suggesting hydrogels potential for promoting tissue regeneration after anti-cancer treatment. The study reveals that PVA/PUL hybrid hydrogels loaded with DOX-PCL-MSs has impactful potential in post-surgical treatment of breast cancer.

Pullulan hydrogels as drug release platforms in biomedicine

Pullulan hydrogels as drug release platforms in biomedicine

Rheological Study of the Formation of Pullulan Hydrogels and Their Use as Carvacrol-Loaded Nanoemulsion Delivery Systems.

Hydrogels have been extensively studied as delivery systems for lipophilic compounds. Pullulan hydrogels were prepared, and their gelation kinetics were studied over time. Pullulan exhibited a relatively slow gelling reaction in basic medium (KOH) using trisodium metaphosphate (STMP) as a cross-linking agent, so capsules cannot be obtained by dripping as easily as in the case of alginate and chitosan. The kinetics of pullulan gelation were studied through rheological analysis over time. An optimal [Pullulan]/[KOH] ratio was found for a fixed [Pullulan]/[STMP] ratio. For this given relationship, gelling time measurements indicated that when the concentration of pullulan increased, the gelation time decreased from 60 min for 6% w/w pullulan to 10 min for 10% w/w. After the gel point, a hardening of the hydrogel was observed over the next 5 h. The formed hydrogels presented high degrees of swelling (up to 1800%). Freeze-dried gels were capable of being rehydrated, obtaining gels with rheological characteristics and visual appearance similar to fresh gels, which makes them ideal to be freeze-dried for storage and rehydrated when needed. The behavior of the hydrogels obtained as active ingredient release systems was studied. In this case, the chosen molecule was carvacrol (the main component of oregano oil). As carvacrol is hydrophobic, it was incorporated into the droplets of an oil-in-water nanoemulsion, and the nanoemulsion was incorporated into the hydrogel. The release of the oil was studied at different pHs. It was observed that as the pH increased (from pH 2 to pH 7), the released amount of carvacrol for the gel with pullulan 10% w/w reached 100%; for the other cases, the cumulative release amount was lower. It was attributed to two opposite phenomena in the porous structure of the hydrogel, where more porosity implied a faster release of carvacrol but also a higher degree of swelling that promoted a higher entry of water flow in the opposite direction. This flow of water prevented the active principle from spreading to the release medium.

Controllable Release of Povidone-Iodine from Networked Pectin@Carboxymethyl Pullulan Hydrogel.

Povidone-iodine (PI) is a common antiseptic reagent which is used for skin infections and wound healing. The control release of PI is quite important to heal the deep and intense wounds. Herein, the preparation of biodegradable pectin@carboxymethyl pullulan (Pe@CMP) hydrogel was carried out and applied for controllable release of PI. CMP was synthesized by interaction of monochloroacetic acid with pullulan at different ratios. The Pe@CMP hydrogel was then prepared by crosslinking of pectin with CMP in presence of glutaraldehyde as cross linker. After carboxymethylation, COOH contents were enlarged to be 24.2–51.2 mmol/kg and degree of substitution was 0.44–0.93. The rheological properties of Pe@CMP hydrogel were enlarged by increment of pectin ratio. Swelling ratio in water (16.0–18.0%) was higher than that of artificial sweat (11.7–13.2%). Pe@CMP hydrogel containing 20% pectin, exhibited the lowest release and 57.7% from PI was released within 360 min. The biological activity of the released PI was monitored to be highly efficient. The kinetic of release was fitted well to the first ordered reaction and Higuchi models. The mechanism of release was explained by the swelling of hydrogel. The networked structure of hydrogel was opened by swelling and PI was released from the outer pores followed by inner pores, achieving the controllable release.

Multilayer fibroin/chitosan oligosaccharide lactate and pullulan immunomodulatory patch for treatment of hernia and prevention of intraperitoneal adhesion

This study aims to develop a novel intraperitoneal two- or three-layered patch with immunomodulatory property for treatment of hernia, regeneration of abdominal wall and prevention of intraperitoneal adhesions. Polypropylene (PP) mesh, middle layer, was intended to provide mechanical support whereas pullulan (PUL) hydrogel coating layer was designed to prevent intraperitoneal adhesions. Fibroin/chitosan oligosaccharide lactate (F/COS) layer electrospun on one side of pullulan was chosen for immunomodulation and abdominal wall regeneration. Physical and mechanical properties and regenerative capacity of intraperitoneal patches were determined. Immunomodulatory property of electrospun layer and whole patch was studied by determining nitric oxide amount produced by RAW 264.7 macrophages. 25 % (w/v) PUL hydrogel and F/COS with 90:10 (w/w) ratio yielded optimal results. Here, we report that fabricated intraperitoneal patches successfully prevented cell adhesion on one side and increased cell viability and proliferation on other side, along with immunomodulation, in vitro.

Methacrylated pullulan/polyethylene (glycol) diacrylate composite hydrogel for cartilage tissue engineering

Pullulan hydrogels are widely used in tissue engineering and drug delivery. However, these hydrogels do not meet the requirements of articular cartilage repair because of their fast degradation rate and poor mechanical strength. Herein, we fabricated a hybrid hydrogel system by combining pullulan with synthetic polymers polyethylene (glycol) diacrylate (PEGDA). In this study, pullulan was modified with methacrylic anhydride (MA) to obtain photo-crosslinkable methacrylated pullulan (PulMA). Moreover, the lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate (LAP) was used as a water-soluble UV photoinitiator to form the PulMA/PEGDA hydrogel by photopolymerization strategy. Compared with the pure PulMA hydrogel, the increase of PEGDA concentration led to a slower degradation rate and an increase of residual mass from 63.9% to 86.8%. There was about 8-fold increase in storage modulus (G′) (reach to 16.0 × 103 Pa) and 13-fold increase in compressive modulus (reach to 1.17 ± 0.17 MPa) with increasing the concentration of PEGDA to 15% (w/v) in the hydrogel. In cell culture in vitro, the rabbit’s mesenchymal stem cells (MSCs) encapsulated in the PulMA/PEGDA hydrogel could adhere and proliferate, indicating that the PulMA/PEGDA hydrogel had a good biocompatibility. Furthermore, the hydrogels supported glycosaminoglycan (GAG) synthesis, and chondrogenic phenotype of MSCs with TGF-β3-containing chondrogenic medium. This study demonstrated that the photo-crosslinking PulMA/PEGDA hydrogels, with good mechanical properties and slow degradation rate are promising scaffolds for cartilage repair and regeneration.

Highly efficient removal of antibiotic from biomedical wastewater using Fenton-like catalyst magnetic pullulan hydrogels

Magnetic nanoparticles that can be employed as Fenton-like catalysts Fenton-like catalysts are attractive materials for degrading antibiotics. In this study, we facilely prepared novel magnetic pullulan (MP) hydrogels by doping modified magnetic nanoparticles into pullulan matrices, which could enhance catalytic degradation performance and strengthen the stability of resulting hydrogels. This is the first time that MP hydrogels have been fabricated successfully and used as Fenton-like catalysts for tetracycline hydrochloride (TCH) degradation. MP hydrogels were characterized and their catalytic TCH degradation abilities were also investigated. The optimized conditions (pH value, Fe3O4 content, H2O2 content and TCH concentration) for TCH degradation were investigated. The optimized system showed excellent degradation efficiency for TCH. Further, the degradation mechanism was comprehensively studied. Finally, synthesized MP hydrogels showed impressive reusability and stability in the cycle experiment. Thus, our findings would open new possibilities to develop magnetic hydrogels in eliminating antibiotic contaminants.

Mussel-inspired magnetic pullulan hydrogels for enhancing catalytic degradation of antibiotics from biomedical wastewater

Magnetic hydrogels are fascinating materials that can be used as Fenton-like catalysts to remove antibiotics from biomedical wastewater. However, the poor distribution of magnetic nanoparticles in hydrogel matrix and weak mechanical properties severely confine their applications from lab to industrial scale. Here, we presented for the first time the facile fabrication of mussel-inspired magnetic pullulan (MMP) hydrogels using polydopamine as a bridge to build a relationship between Fe3O4 and pullulan matrix, which could solve the common problems of magnetic hydrogels and enhance catalytic degradation of tetracycline (TC) simultaneously. Degradation results proved that our catalytic system (MMP4) showed superior TC degradation efficiency (86.32% within 60 min). Theoretical studies verified that TC could act as an electron donor and the produced electrons from TC were transferred via polydopamine to the iron species through π-Fe interactions. Besides, MMP4 exhibited excellent reusability and stability that no apparent decrease in degradation efficiency was observed after 5 cycles. Altogether, our findings provide a simple but effective strategy to design magnetic hydrogel catalysts for enhancing antibiotic degradation from biomedical wastewater.

Effect of pullulan concentration and pH on the interactions between whey protein concentrate and pullulan during gelation.

Whey protein concentrate (WPC)/pullulan (PUL) hydrogel is applied as a microencapsulation wall material to protect probiotics. However, the interactions between WPC and PUL during gelation have not been clarified. In the present study, the effects of PUL concentration and pH on the interactions between WPC and PUL during gelation were evaluated with respect to appearance, zeta-potential, sulfhydryl group amount, surface hydrophobicity and infrared spectroscopy measurements. The rheological properties of WPC/PUL gels were also determined. The results obtained showed that a proper concentration (0.40 g mL-1 ) of PUL could improve the gel by enhancing the strength of hydrogen bonding, electrostatic interactions and exposure of hydrophobic groups, whereas too much PUL inhibited the formation of disulfide bonds. Furthermore, hydrophobic interactions, disulfide bonds and hydrogen bonds were destroyed in varying degrees under an alkaline environment. The rheological results also demonstrated a similar effect of PUL concentration and pH on the storage modulus (G') of WPC/PUL gels. When the WPC/PUL gel was formed at PUL concentration of 0.40 g mL-1 and pH 7.0, the interaction between WPC and PUL could be enhanced, which is beneficial for the future application of WPC/PUL gels in the food industry. © 2020 Society of Chemical Industry.

Facile fabrication of functional hydrogels consisting of pullulan and polydopamine fibers for drug delivery

With the rapid development of biomedicine applications, more flexible and efficient fabrication strategies are required for drug delivery vehicles. Naturally resourced polymers have gained considerable attention for construction of drug carriers. Here, biocompatible hydrogel reservoir system (named PHG-PDA) based on pullulan and polydopamine (PDA) are designed and fabricated by one-pot incorporation of PDA fibers into pullulan hydrogel (PHG). The structure and performance of the PHG-PDAs can be nicely adjusted by regulating the content of PDA fibers in precursor hydrogel solutions. Crystal violet is used as a drug prototype and introduced into hydrogels via swelling-diffusion approach. We found that the drug loading process followed the pseudo-second-order model and Langmuir isotherm model, while the drug releasing process was pH-responsive, and the cumulative release reached 60.3% and 87% at pH 7.4 and 5.0, respectively. In vitro cytotoxicity studies on L929 cells demonstrated that our hydrogels were nontoxic even in a high concentration (3.4 mg/mL). In sum, these biocompatible PHG-PDAs with tunable physicochemical properties are promising systems for drug delivery.

Polydopamine/montmorillonite-embedded pullulan hydrogels as efficient adsorbents for removing crystal violet

Both secondary pollution and the low mechanical strength of adsorbents have severely impeded the practical application of adsorption methods in the dye wastewater treatment. In this work, we innovatively synthesized a composite hydrogel adsorbent by incorporating polydopamine (PDA) and montmorillonite (MMT) into the pullulan hydrogel matrix for dye adsorption. First, the successful formation of the resultant adsorbents was verified by Fourier-transform infrared spectroscopy and scanning electron microscope elemental mapping analysis. Then, several physicochemical properties (such as thermal and swelling properties, microarchitecture, and mechanical strength) of the five prepared adsorbents (PM1–PM5) were investigated. These results demonstrated the adsorbents had tunable properties, which can be achieved by adjusting the PDA/MMT mass ratio. Next, the dye adsorption performance was systematically explored. The resultant adsorbent (PM3) had a maximum adsorption capacity of 112.45 mg/g and its adsorption data was best described by a Langmuir isotherm and pseudo-second-order kinetic. Finally, the adsorption mechanisms and potential commercial practicability of the adsorbent were studied. Altogether, the designed adsorbent could effectively avoid generating the secondary pollution typical of adsorbents and it displayed excellent mechanical strength, thus opening up a new horizon in mitigating environmental pollution from textile industries.

Crosslinked nanogel-based porous hydrogel as a functional scaffold for tongue muscle regeneration

Surgical resection in tongue cancer can impair speech and swallowing, reducing quality of life. There is a need for biomaterials that can regenerate tongue muscle tissue defects. Ideally, such a biomaterial would allow controlled release of therapeutic proteins, support the survival and differentiation of therapeutic cells, and promote tongue muscle regeneration in vivo. The aim of the current study was to assess these factors in an acryloyl group-modified crosslinked nanogel, consisting of cholesterol-bearing pullulan hydrogel nanoparticles, to determine its potential as a regenerative therapeutic following tongue resection. The hydrogel demonstrated substantial porosity and underwent slow biodegradation. When loaded with a model protein, the gel enabled sustained protein release over two weeks in serum, with no initial burst release. Mouse myoblasts demonstrated adhesion to the hydrogel and cell survival was observed up to one week. Gel-encapsulated myoblasts demonstrated normal myotube differentiation. Myoblast-loaded gels were implanted in a tongue defect in mice, and there was a significant increase in newly-regenerated myofibers in gel-implanted animals. The developed biomaterial platform demonstrates significant potential as a regenerative treatment following tongue resection, as it facilitates both protein and cell-mediated therapy, and stimulates tongue muscle regeneration in vivo.

Soft and highly responsive multi-walled carbon nanotube/pullulan hydrogel composites as electroactive materials

Pullulan is a polysaccharide as obtained from the black yeast fermentation. Soft and flexible pullulan hydrogels and multi-walled carbon nanotube/pullulan hydrogel composites were fabricated by a solvent casting method. The effects of crosslinking agent, MWCNT content, and electric field strength on the electromechanical behaviours were investigated. The storage modulus (G′) or the elasticity monotonically increased with increasing crosslinking agent and electric field strength. The MWCNT/pullulan hydrogel composite with 0.01%v/v MWCNT provided the highest storage modulus sensitivity of 71.2 at the applied electric field strength of 800 V/mm, relative to other hydrogel composites previously reported. The storage and loss moduli were further transformed to the creep compliance through the relaxation spectrum and the retardation spectrum, respectively. The creep compliance of the pristine hydrogels and composites decreased with increasing crosslinking agent amount and electric field strength. The 01MWCNT/Pullulan_5STMP hydrogel composite yielded the lowest creep compliance function, illustrating the ability to resist deformation through electric field. The dielectrophoresis force density of the MWCNT/pullulan hydrogel composite with 0.01%v/v MWCNT was the highest obtained at 0.2258 mN/mm3, suggesting as the most suitable for practical actuator applications.

Topical film prepared with Rhus verniciflua extract-loaded pullulan hydrogel for atopic dermatitis treatment.

Atopic dermatitis (AD) is characterized by relapsing pruritus and skin dryness. Due to the pathogenic multiplicity and the adverse effects associated with the current therapeutics, development of transdermal drug delivery system is becoming an area of interest. Here, a novel topical film prepared with Rhus verniciflua extract (RVE)-loaded pullulan hydrogel (RVE@PH) was synthesized and tested its therapeutic efficacy on the AD rats modeled by neonatal capsaicin injection method. The RVE@PH was characterized by a Fourier-transform infrared spectroscopy and an in vitro release assay. Rat pups were randomly divided into two groups: vehicle-treated (VEH; n = 5) and capsaicin-treated (n = 15). The latter were given capsaicin subcutaneously at 24 h after birth for AD induction and further divided into three groups (n = 5 per each): not treated (CAP), pullulan hydrogel-applied (PH), and RVE@PH-applied (RVE-PH). The pullulan hydrogel and RVE@PH were topically applied on shoulder lesions for 14 days (from 42 to 56 days after birth). Their phenotypes were compared based on the dermatitis score, epidermal thickness, mast cell infiltration, and serum myeloperoxidase (MPO) activities. The PH group showed significant attenuation in all the aforementioned values compared to the CAP group, suggesting that pullulan hydrogel itself has therapeutic activity against AD. Notably, the attenuations were more potent in the RVE-PH group than the PH group, indicating that the therapeutic efficacy against AD is augmented by the presence of RVE, a loaded pharmaceutic. Collectively, these results indicate that RVE@PH inhibits AD through exerting the dual roles, that is, the pullulan hydrogel-mediated physical and RVE-mediated pharmaceutical actions. © 2019 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 2325-2334, 2019.

Enzymatically crosslinked and mechanically tunable silk fibroin/pullulan hydrogels for mesenchymal stem cells delivery

Hydrogels with good biocompatibility, proper degradation rates, and tissue-matched elasticity are widely used in tissue engineering, regenerative medicine, and drug delivery. In this study, enzymatically crosslinked biocompatible hydrogels were successfully developed using silk fibroin (SF) and pullulan (PL) under physiological conditions in the presence of both horseradish peroxidase and hydrogen peroxide. A series of properties of the hydrogels including gelation time, equilibrium swelling, enzyme degradation, morphology, rheological property, and compression modulus of SF/PL hydrogels were studied by varying the concentration of PL. The results showed that the SF/PL hydrogels had applicable gel-forming rate (ranging from 12 to 60 min), tunable compressive strength (ranging from 7 to 71 kPa) and shear mechanical properties (ranging from 200 to 1470 Pa). The properties of the SF/PL hydrogels were easily modulated by changing the concentration of PL. The compressive modulus of the SF + 20%PL hydrogels was 71.4 ± 9.3 kPa, which was in the range of that of musculoskeletal system. In addition, the rabbit bone marrow-derived mesenchymal stem cells were encapsulated in SF/PL hydrogels for 7 days, and cell viability and morphology were observed. Live/dead staining assay demonstrated that the hydrogel system possessed good cytocompatibility. These features support that SF/PL hydrogels have a potential as cell delivery scaffold in musculoskeletal tissue engineering.