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1.
Excellent radiation resistance is a prerequisite for pressure-sensitive hydrogels to be used in high-energy radiation environments. In this work, tannic acid-modified boron nitride nanosheet(BNNS-TA) is first prepared as the radiation-resistant additive by a facile one-step ball milling of hexagonal boron nitride and tannic acid. Then, polyacrylamide(PAAm)-based pressure-sensitive hydrogel doped with BNNS-TA and Fe3+ions is fabricated. The ternary BNNS-TA/Fe3+/PAAm hydrogel...  相似文献   

2.
The efficiency of antitumor immunotherapy is usually limited by the immunosuppressive tumor microenvironment (TME). In this study, we developed a chemo-immunotherapy strategy that is able to improve the immunosuppressive TME for enhancing the antitumor efficacy. The chemo-immunotherapy was achieved by the topical co-delivery of a chemotherapeutic drug, Doxorubicin (DOX), an immune checkpoint blocking antibody targeting programmed cell death protein 1 (aPD-1), and an indoleamine-2,3-dioxygenase (IDO) inhibitor, 1-methyl-d -tryptophan (d -1MT) by using a thermosensitive polypeptide hydrogel. It was revealed that the sustained DOX release from the hydrogel caused the immunogenic cell death (ICD) of B16F10 cells in vitro, and the tumor cell lysates subsequently promoted the activation of dendritic cells (DCs). After intratumoral injection into B16F10 melanoma-bearing mice, the DOX/aPD-1/D-1MT co-loaded hydrogel exhibited enhanced tumor inhibition efficacy and prolonged animal survival time, compared to the DOX/aPD-1/D-1MT mixed solution, DOX-loaded hydrogel or DOX/aPD-1 co-loaded hydrogel. The improvement of immunosuppressive TME and enhancement of antitumor immune response after the local chemo-immunotherapy were demonstrated by the augmented activation of DCs and increased infiltration of CD8+ and CD4+ T cells, as well as enhanced secretion of pro-inflammatory cytokines. Therefore, the hydrogel-based local chemo-immunotherapy system holds great potential for effective antitumor treatment.  相似文献   

3.
邵正中 《高分子科学》2017,35(4):515-523
A simple and facile synthetic methodology for fabricating the regenerated silk fibroin(RSF)-based hydrogel which consisted of the in situ generated magnetic ferriferous oxide(Fe_3O_4) was developed. Using the co-precipitation of Fe~(2+) and Fe~(3+) within the RSF-based hydrogel with 90% RSF and 10% HPMC(hydroxypropyl methyl cellulose), the as-prepared RSF/Fe_3O_4 hydrogel not only showed high strength of saturation magnetization, but also exhibited excellent catalytic activities. For example, with the assistant of 3,3′,5,5′-tetramethylbenzidine(TMB), the RSF/Fe_3O_4 hydrogel could detect H_2O_2 at a concentration as low as 1 × 10~(-6) mol·L~(-1). In addition, the catalytic activities were able to be maintained for a long term under various conditions. These findings suggest that the RSF-based materials can be endowed with interesting properties, and have great potential for the applications in the fields of biotechnology and environmental chemistry.  相似文献   

4.
Exogenous FeIII can be used for cancer magnetic resonance (MR) imaging and potentially for cancer treatment by a ferroptosis pathway or photothermal ablation. To achieve this, effective and accurate delivery of FeIII to cancerous sites is critical, requiring a balance of release kinetics of Fe3+ in tumorous and normal tissues. A nanoprobe is described consisting of upconversion luminescence (UCL) nanoparticles as a core and a coordinatively unsaturated FeIII‐containing Fe3+/gallic acid complex as a shell. Owing to the introduction of an unsaturated coordination structure, FeIII in the nanoprobe can be released only in the tumor microenvironment in response to the lightly acidic pH. The multiple UCLs are used for quantitatively visualizing the release of Fe3+ in vivo, whilst the release resultant serves as a photothermal agent. This nanoprobe exhibited ligand‐free tumor targeting ability, activatable MR imaging performance, and efficacious therapeutic effects against tumors in vivo.  相似文献   

5.
In this study, we report pH-responsive metal-based biopolymer nanoparticles (NPs) for tumor-specific chemotherapy. Here, aminated hyaluronic acid (aHA) coupled with 2,3-dimethylmaleic anhydride (DMA, as a pH-responsive moiety) (aHA-DMA) was electrostatically complexed with ferrous chloride tetrahydrate (FeCl2/4H2O, as a chelating metal) and doxorubicin (DOX, as an antitumor drug model), producing DOX-loaded Fe-based hyaluronate nanoparticles (DOX@aHA-DMA/Fe NPs). Importantly, the DOX@aHA-DMA/Fe NPs improved tumor cellular uptake due to HA-mediated endocytosis for tumor cells overexpressing CD44 receptors. As a result, the average fluorescent DOX intensity observed in MDA-MB-231 cells (with CD44 receptors) was ~7.9 × 102 (DOX@HA/Fe NPs, without DMA), ~8.1 × 102 (DOX@aHA-DMA0.36/Fe NPs), and ~9.3 × 102 (DOX@aHA-DMA0.60/Fe NPs). Furthermore, the DOX@aHA-DMA/Fe NPs were destabilized due to ionic repulsion between Fe2+ and DMA-detached aHA (i.e., positively charged free aHA) in the acidic environment of tumor cells. This event accelerated the release of DOX from the destabilized NPs. Our results suggest that these NPs can be promising tumor-targeting drug carriers responding to acidic endosomal pH.  相似文献   

6.
Guanosine‐5′‐hydroxamic acid ( 3 ) forms hydrogels when mixed with guanosine ( 1 ) and KCl. The 5′‐hydroxamic acid (HA) unit is pH‐responsive and also chelates Fe3+. When gels are prepared under basic conditions, the 5′‐HA groups are deprotonated and the anionic hydrogel binds cationic thiazole orange (TO), signaled by enhanced fluorescence. The HA nucleoside 3 , when immobilized in the G‐quartet gel, acts as a supramolecular siderophore to form red complexes with Fe3+. We patterned the hydrogel's surface with FeCl3, by hand and by using a 3D printer. Patterns form instantly, are visible by eye, and can be erased using vitamin C. This hydrogel, combining self‐assembled G‐quartet and siderophore–Fe3+ motifs, is strong, can be molded into different shapes, and is stable on the bench or under salt water.  相似文献   

7.
In this study, a unique magnetic, pH, and thermo‐responsive hydrogel nanocomposite was synthesized via surface reversible addition fragmentation chain transfer (RAFT) copolymerization of acrylic acid (AA) and N‐isopropyl acrylamide (NIPAM) in the presence of magnetic β‐cyclodextrin (β‐CD). The nanocomposite demonstrated a pH‐responsiveness behavior at pHs 3 and 9. Moreover, swelling behaviors of nanocomposite were measured in solutions with various temperatures. Furthermore, the nanocomposites exhibited high swelling capacity by applying an external magnetic field because of the presence of Fe3O4 nanoparticles in the polymer structure. Besides, the doxorubicin (DOX) loading and releasing behaviors of the hydrogel nanocomposites were studied because of the stimuli‐responsive properties of the synthesized carriers. The adsorption of DOX obeyed a pseudo‐second‐order model and fitted well to the Langmuir isotherm model with the maximum adsorption capacity uptake of 291 mg g?1. In conclusion, the hydrogel nanocomposites were found to be as potential nanocarriers for use in controlled release applications.  相似文献   

8.
The irradiation of tumors in radiotherapy requires accurate 3D dosimetry. The Fricke 3D dosimeters, which were considered to be high potential of application in 3D dosimetry, suffer from a reduced temporal integrity of dose distribution caused by Fe3+ ions diffusion. To overcome the drawback, we firstly synthesized a kind of amphiphilic molecules with critical micelle concentration of 0.45 g/L and hydrophile‐lipophile balance value of 10, then prepared multiple emulsions by self‐assembling those molecules in Fricke solution under liquid paraffin, and finally obtained Fricke hydrogel embedded with the multiple emulsions. The diffusion coefficient of Fe3+ ions in the embedded Fricke hydrogel was measured to be 0.17 mm2/h. The hydrogel dosimeter exhibits considerable potential for use in dose verification applications.  相似文献   

9.
Cancer is one of the major diseases that seriously threaten human health. Drug delivery nanoplatforms for tumor treatment have attracted increasing attention owing to their unique advantages such as good specificity and few side effects. This study aimed to fabricate a pH-responsive drug release multifunctional nanoplatform NaGdF4:Yb,Er,Fe@Ce6@mSiO2-DOX. In the platform, Fe3+ doping enhanced the fluorescence intensity of NaGdF4:Yb, Er by 5.8 folds, and the mSiO2 shell substantially increased the specific surface area of nanomaterials (559.257 m2/g). The loading rates of chlorin e6 and doxorubicin hydrochloride (DOX) on NaGdF4:Yb,Er,Fe@Ce6@mSiO2-DOX reached 28.58 ± 0.85% and 87.53 ± 5.53%, respectively. Additionally, the DOX release rate from the nanoplatform was only 24.4% after 72 h at pH 7.4. However, under tumor microenvironment conditions (pH 5.0), the release rate of DOX increased to 85.3% after 72 h. The nanoplatform could generate reactive oxygen species (ROS) under 980 nm near-infrared excitation. Moreover, the nanoplatform exhibited a strong comprehensive killing efficiency against cancer cells. The viabilities of HeLa, MCF-7, and HepG2 cancer cells were only 18.5, 11.4, and 9.3%, respectively, after being treated with a combination of photodynamic therapy and chemotherapy. The constructed nanoplatform exhibits great application potential in cancer treatment.  相似文献   

10.
Forming carboxyl-Fe3+ coordination bonds as physical crosslinks is an effective strategy to develop tough hydrogels. Considering the inhibition of ferric ions on free-radical polymerization, these coordination bonds cannot be formed during the reaction, and a soaking process of preformed hydrogels is usually required for mechanical enhancement, resulting in uncontrollable gradient structure, long preparation time, and unnecessary waste of metallic ions. A facile strategy is reported here to prepare tough metallosupramolecular hydrogels by polymerization and in situ formation of coordination bonds with phosphates as the temporal ligands of Fe3+ ions. The phosphate ligands in the precursor solution form coordination complexes with the Fe3+ ions, which avoids the inhibition and ensures the polymerization. After swelling the resultant hydrogel in water, the ligands are substituted by carboxyl groups of the gel matrix due to the variation of local pH. The equilibrated hydrogel with carboxyl-Fe3+ coordination bonds as the physical crosslinks possesses excellent mechanical properties that can be tuned over a wide range by adjusting the polymer compositions and the concentrations of phosphate ligands and Fe3+ ions. This strategy should be applicable to other systems to enable synthesis of functional hydrogels with Fe3+ ions as the additive toward specific applications in engineering and biomedical fields.  相似文献   

11.
We report a facile fabrication of a host–metal–guest coordination‐bonding system in a mesostructured Fe3O4/chitosan nanoparticle that can act as a pH‐responsive drug‐delivery system. The mesostructured Fe3O4/chitosan was synthesized by a solvothermal approach with iron(III) chloride hexahydrate as a precursor, ethylene glycol as a reducing agent, ammonium acetate as a porogen, and chitosan as a surface‐modification agent. Subsequently, doxorubicin (DOX), acting as a model drug (guest), was loaded onto the mesostructured Fe3O4/chitosan nanoparticles, with chitosan acting as a host molecule to form the NH2? ZnII? DOX coordination architecture. The release of DOX can be achieved through the cleavage of coordination bonds that are sensitive to variations in external pH under weakly acidic conditions. The pH‐responsive nature of the nanoparticles was confirmed by in vitro releases and cell assay tests. Furthermore, the relaxation efficiency of the nanoparticles as high‐performance magnetic resonance imaging contrast agents was also investigated. Experimental results confirm that the synthesized mesostructured Fe3O4/chitosan is a smart nanovehicle for drug delivery owing to both its pH‐responsive nature and relaxation efficiency.  相似文献   

12.
《中国化学快报》2023,34(10):108262
To achieve smart and personalized medicine, the development of hydrogel dressings with sensing properties and biotherapeutic properties that can act as a sensor to monitor of human health in real-time while speeding up wound healing face great challenge. In the present study, a biocompatible dual-network composite hydrogel (DNCGel) sensor was obtained via a simple process. The dual network hydrogel is constructed by the interpenetration of a flexible network formed of poly(vinyl alcohol) (PVA) physical cross-linked by repeated freeze-thawing and a rigid network of iron-chelated xanthan gum (XG) impregnated with Fe3+ interpenetration. The pure PVA/XG hydrogels were chelated with ferric ions by immersion to improve the gel strength (compressive modulus and tensile modulus can reach up to 0.62 MPa and 0.079 MPa, respectively), conductivity (conductivity values ranging from 9 × 10−4 S/cm to 1 × 10−3 S/cm) and bacterial inhibition properties (up to 98.56%). Subsequently, the effects of the ratio of PVA and XG and the immersion time of Fe3+ on the hydrogels were investigated, and DNGel3 was given the most priority on a comprehensive consideration. It was demonstrated that the DNCGel exhibit good biocompatibility in vitro, effectively facilitate wound healing in vivo (up to 97.8% healing rate) under electrical stimulation, and monitors human movement in real time. This work provides a novel avenue to explore multifunctional intelligent hydrogels that hold great promise in biomedical fields such as smart wound dressings and flexible wearable sensors.  相似文献   

13.
Sodium alginate (AlgNa) and poly(diallyldimethylammonium chloride) (PDDA) were mixed to obtain an interpenetrating polymer composite via electrostatic interaction and then cast on an Au electrode surface, followed by incorporation of metal ions (e.g. Fe3+ or Ca2+, to form AlgFe or AlgCa hydrogel) and glucose oxidase (GOx) (or lactate oxidase (LOx)), to prepare amperometric enzyme electrodes. The interactions of PDDA, Alg, and Fe3+ are studied by visual inspection as well as microscopic and electrochemical methods. Under optimized conditions, the PDDA-AlgFe-enzyme/Au and PDDA-AlgCa-enzyme/Au electrodes can give good analytical performance (e.g. nM-scale limit of detection of glucose or lactate, and sensitivities > 50 μA cm−2 mM−1) in the first-generation biosensing mode, which are better than the reported analogs using typical polysaccharide biopolymers as enzyme-immobilization matrices. The enzyme electrodes also worked well in the second-generation biosensing mode in the coexistence of p-benzoquione or ferrocene monocarboxylic acid artificial mediator. Biofuel cells (BFCs) with the enzyme electrodes as the bioanodes and glucose (or lactate) as the biofuel were also fabricated with satisfactory results. The proposed protocols for preparation of high performance Alg-based biocomposites may find wide applications in bioanalysis.  相似文献   

14.
Inducing high levels of reactive oxygen species (ROS) inside tumor cells is a cancer therapy method termed chemodynamic therapy (CDT). Relying on delivery of Fenton reaction promoters such as Fe2+, CDT takes advantage of overproduced ROS in the tumor microenvironment. We developed a peptide-H2S donor conjugate, complexed with Fe2+, termed AAN - PTC – Fe2+ . The AAN tripeptide was specifically cleaved by legumain, an enzyme overexpressed in glioma cells, to release carbonyl sulfide (COS). Hydrolysis of COS by carbonic anhydrase formed H2S, an inhibitor of catalase, an enzyme that detoxifies H2O2. Fe2+ and H2S together increased intracellular ROS levels and decreased viability in C6 glioma cells compared with controls lacking either Fe2+, the AAN sequence, or the ability to generate H2S. AAN - PTC – Fe2+ performed better than temezolimide while exhibiting no cytotoxicity toward H9C2 cardiomyocytes. This study provides an H2S-amplified, enzyme-responsive platform for synergistic cancer treatment.  相似文献   

15.
Theranostic platform including therapeutic agent and diagnostics factor is of great interest in the current cancer treatment research. In this study, we constructed a pH-responsive nanomagnetic hydrogel based on chitosan, hyaluronic acid, and glucose oxidase (NMH-CsHA-GOx) as a platform, which represents good performance both as a nanomedicine and as a dual-modal magnetic resonance imaging (MRI) contrast agent. The NMH-CsHA-GOx is a hybrid catalyst that catalyzes a cascade reaction that results in the production of hydroxyl radicals. This leads to the apoptosis and death of cancer cells under the mildly acidic TME. Moreover, the ultrasmall superparamagnetic Fe3O4 NPs act as the T1-weighted and T2-weighted (dual-modal) MRI contrast agents that can be used to identify the cancer cells. The r1 = 6.37, r2 = 27.07/mM/s, and r2/r1 ratio were obtained from MRI relaxivity measurements. The NMH-CsHA-GOx was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and vibrating sample magnetometry (VSM). The morphology of the hydrogel and nanomagnetic hydrogel were characterized by Field emission scanning electron microscopy (FESEM). The size and distribution of Fe3O4NPs were studied by Transmission electron microscopy (TEM) and X-ray elemental mapping, respectively. The analysis confirmed the very small size of the Fe3O4 NPs (5–12 nm), which were dispersed uniformly. The NMH-CsHA-GOx represents high selectivity between normal cells (L929 mouse fibroblast cell line) and tumor cells (MCF-7 breast cancer cell line). The pH-sensitive NMH-CsHA-GOx, can produce a controlled amount of hydroxyl radical under the mildly acidic TME.  相似文献   

16.
Sono-immunotherapy holds great potential for deep tumor inhibition; however, smart sono-therapeutic agents to simultaneously eliminate ‘domestic’ tumor cells and regulate the ‘community’ tumor immune microenvironment have rarely been developed. Herein, we report a spatiotemporally controllable semiconducting iron-chelated nano-metallomodulator (SINM) for hypersensitive sono-metallo-immunotherapy of cancer. SINM consists of a semiconducting polymer (SP) backbone chelating iron ions (Fe3+) with thiophene-based Schiff base structure, and a hydrophilic side chain. Upon accumulation in tumors after systemic administration, SINM specifically arouses ferroptosis and M1 macrophage polarization due to its response toward the tumor redox environment; meanwhile, the chelation of Fe3+ enhances the sono-sensitizing effect of SPs, leading to enhanced generation of reactive oxygen species for immunogenic cell death. Such combined sonodynamic metallo-immunotherapy of SINM efficiently ablates deep tumor and spatiotemporally regulates immunophenotypes.  相似文献   

17.
Aggregation is an economical and widely existing method to in hematite mineral processing. In order to achieve the aggregation of hematite particles, high-efficiency agents are required. In this work, the xanthan gum (XG) and Fe3+ were used to explore its aggregation effect on the fine hematite particles. The settling and adsorption experiments were conducted on hematite with XG in the absence and presence of Fe3+. The results show that it is difficult to settle hematite with XG alone, and XG exhibits excellent performance with the mass ratio of 2/1 (XG/ FeCl3) at pH 2–10 in the presence of Fe3+. Zeta potential measurements, Fourier transform infrared (FTIR), Microscope and X-ray photoelectron spectroscopy (XPS) analyses were performed to detect the underlying mechanism. The zeta potential, solution chemistry and FTIR analyses results show that the co-adsorption of XG, Fe(OH)2+, Fe(OH)2+ and Fe3+ is found on hematite surface through specific and electrostatic adsorption, respectively, and the hematite surface is also covered by Fe(OH)3(s) precipitation turned by Fe3+. XPS spectral investigations and microscope observations provide evidence in support of coordination interaction between ferric ions active sites and XG. In addition, the aggregation model of fine hematite particles suspension using XG in the presence of Fe3+ was drawn.  相似文献   

18.
The retention, release, and detection of metallic complexes in polymeric hydrogels are of interest in drug delivery, analytical chemistry, and water remediation. The electrochemistry of the redox complexes inside the hydrogel could be affected by the viscoelastic properties of the gel, local ionic force and pH, and interactions (e.g., hydrophobic) between the complex and the polymer chains. In this work, it is shown that a simple setup, consisting of a disk electrode pressed on the hydrogel, allows to perform electrochemistry of a redox couple: Tris(1,10-phenanthroline)iron(II) (Fe(phen)3 2+) inside a hydrogel matrix. The behavior is compared with the same couple in solution, and it is found that the electrochemical properties of the redox couple are strongly affected by the presence of the hydrogel matrix. The cyclic voltammogram of the hydrogel loaded with complex shows a response, which suggests electrochemical-chemical mechanism. The chemical step is likely linked to a catalytic oxidation of free hydrated Fe2+ ions present inside the hydrogel together with the redox complex. Since Fe2+ ions have small charge transfer constants on the glassy carbon electrodes, only the catalytic current is observed. Indeed, when excess ligand (phenanthroline) is absorbed inside the hydrogel, the measured cyclic voltammograms show a single reversible oxidation/reduction step. It seems that the complexation equilibrium shifts toward the complex, making the free iron concentration negligible. Accordingly, the cyclic voltammetry shape and peak potential difference agree with a reversible oxidation/reduction. Additionally, the peak currents of the cyclic voltammograms show a linear dependence with the square root of time, as predicted by a Randles-Sevcik equation. However, the measured currents are smaller than the simulated ones. The differences are in agreement with simulations of the cyclic voltammograms where the migration of the redox species is considered. Chronoamperometry is used to measure the mass transport of redox species inside the hydrogel. It is found that the current transients still obey Cottrell’s equation, but the diffusion coefficients obtained from the slopes of Cottrell’s plots have to be corrected for migration effects. The effective diffusion coefficient of Fe(phen)3 2+ measured inside the hydrogel (D Red-hydrogel = 5.5 (±0.5) × 10?8 cm2 s?1) is ca. 80 times smaller than the one measured in solution (D Red-solution = 4.4 (±0.5) × 10?6 cm2 s?1). The simple setup has a true semi-infinite boundary condition, which allows characterizing the hydrogel in the same condition as the bulk material and easily changing both the redox species and the hydrogel structure.  相似文献   

19.
Small (2–28 nm) NaREF4 (rare earth (RE)=Nd–Lu, Y) nanoparticles (NPs) were prepared by an oil/water two‐phase approach. Meanwhile, hydrophilic NPs can be obtained through a successful phase‐transition process by introducing the amphiphilic surfactant sodium dodecylsulfate (SDS) into the same reaction system. Hollow‐structured NaREF4 (RE=Y, Yb, Lu) NPs can be fabricated in situ by electron‐beam lithography on solid NPs. The MTT assay indicates that these hydrophilic NPs with hollow structures exhibit good biocompatibility. The as‐prepared hollow‐structured NPs can be used as anti‐cancer drug carriers for drug storage/release investigations. Doxorubicin hydrochloride (DOX) was taken as model drug. The release of DOX from hollow α‐NaLuF4:20 % Yb3+, 2 % Er3+ exhibits a pH‐sensitive release patterns. Confocal microscopy observations indicate that the NPs can be taken up by HeLa cells and show obvious anti‐cancer efficacy. Furthermore, α‐NaLuF4:20 % Yb3+, 2 % Er3+ NPs show bright‐red emission under IR excitation, making both the excitation and emission light fall within the “optical window” of biological tissues. The application of α‐NaLuF4:20 % Yb3+, 2 % Er3+ in the luminescence imaging of cells was also investigated, which shows a bright‐red emission without background noise.  相似文献   

20.
Carbon dot (CD)-based multi-mode sensing has drawn much attention owing to its wider application range and higher availability compared with single-mode sensing. Herein, a simple and green methodology to construct a CD-based dual-mode fluorescent sensor from the waste biomass of flowers of wintersweet (FW-CDs) for parallel and semi-quantitative visual detection of Cr(VI) and Fe3+ was firstly reported. The FW-CD fluorescent probe had a high sensitivity to Cr(VI) and Fe3+ with wide ranges of linearity from 0.1 to 60 µM and 0.05 to 100 µM along with low detection limits (LOD) of 0.07 µM and 0.15 µM, respectively. Accordingly, the FW-CD-based dual-mode sensor had an excellent parallel sensing capacity toward Cr(VI) and Fe3+ with high selectivity and strong anti-interference capability by co-using dual-functional integration and dual-masking strategies. The developed parallel sensing platform was successfully applied to Cr(VI) and Fe3+ quantitative detection in real samples with high precision and good recovery. More importantly, a novel FW-CD-based fluorescent hydrogel sensor was fabricated and first applied in the parallel and semi-quantitative visual detection of Cr(VI) and ferrous ions in industrial effluent and iron supplements, further demonstrating the significant advantage of parallel and visual sensing strategies.  相似文献   

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