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1.
In this work, we developed a modified calcination and extraction method to obtain controllable micro/mesoporous nanoparticle samples POSS–MPS, which were synthesized through glycidyl polyhedral oligomeric silsesquioxane (G-POSS) grafting with aminopropyl-functionalized mesoporous silica (AP-MPS). The POSS–MPS was introduced into the cyanate ester (CE) matrix to optimize the dielectric properties and enhance the toughness of the POSS–MPS/CE nanocomposite. The structure of the hybrid was characterized by FTIR and SEM. The dispersion properties, mechanical properties, dielectric properties and thermal performance were also studied. The results showed that both the C-POSS–MPS and E-POSS–MPS uniformly distribute in the CE matrix with the content of 0.5–4 wt%. The impact strength increased 52% and 60% separately with 2 wt% C-POSS–MPS and E-POSS–MPS addition respectively. The introduction of E-POSS–MPS particles can significantly decrease the dielectric loss value of the POSS–MPS/CE composites to 0.00498, which is of potential in wave transparent composites and structures.

A promising method to improve the performance of CE composites via combining advantages of POSS and MPS.  相似文献   

2.
To design a mechanically stable and superhydrophobic coating, a polyhedral oligomeric silsesquioxane (POSS)-containing poly(perfluoropolyether)methacrylate (PFPEM) hybrid copolymer (PFPEM–POSS) was synthesized via a free-radical solution polymerization with PFPEM, 1H,1H,2H,2H-perfluorooctyl acrylate, methyl (meth)acrylate, n-butyl acrylate, hydroxypropyl acrylate, methacryloxy propyl trimethoxy silane, and methacrylisobutyl POSS; and azobisisobutyronitrile as an initiator. Hydrophobic coatings were formed on substrates by a facile one-step dip-coating method in a solution mixture of diethylene glycol dimethyl ether with the PFPEM–POSS hybrid copolymer. The chemical structure of the PFPEM–POSS copolymer and the surface morphology and performance of the PFPEM–POSS coatings were investigated. The results indicate that, under POSS aggregation via the fluorophilic/oleophilic co-monomer phase separation and owing to the low-surface-energy poly(perfluoropolyether)methacrylate incorporated into the copolymer, PFPEM–POSS exhibited a hierarchical micro-nano roughness in atomic force microscopy observations and provided the treated substrates with excellent hydrophobicity and abrasion resistance. As a result, the water contact angle reached 152.3° on the treated glass.

A coating with excellent superhydrophobicity and durability was built via incorporating an environmentally-friendly poly(perfluoropolyether)methacrylate copolymer into polyhedral oligomeric silsesquioxane (POSS).  相似文献   

3.
We prepared poly(N-isopropylacrylamide-co-4-tert-butylcalix[8]arene) (PNIPAM-TBCX) hydrogels by copolymerization of N-isopropylacrylamide (NIPAM) with 4-tert-butylcalix[8]arene (TBCX) to capture hazardous pentachlorophenol (PCP) from aqueous solution. Adsorption experiments showed that the adsorption capacities of PNIPAM-TBCX hydrogels reached 1.96, 2.08 and 2.02 mg PCP per 1 g of hydrogel, while the molar percentage ratio of TBCX in the hydrogels was as low as 0.5%, 0.7% and 1%. The equilibrium adsorption of PCP on the hydrogels was studied using different adsorption models. In addition, the PNIPAM-TBCX hydrogel still retained its performance when regenerated several times by immersing in water at 323 K.

We synthesized 4-tert-butylcalix[8]arene modified poly(N-isopropylacrylamide) hydrogels to enhance the adsorption ability for pentachlorophenol in aqueous solutions.  相似文献   

4.
The simple sorting procedure and continuous use of poly(N-isopropylacrylamide) (PNIPAM), a well-known thermoresponsive polymer, have a high potential for the mass production of single-walled carbon nanotubes (SWCNTs) with a specific electronic structure. However, knowledge of efficient single-chirality sorting methods with mixed surfactant systems is not applicable. In this work, we explored experimental conditions by controlling the interaction among PNIPAM, sodium cholate (SC) and SWCNTs. An optimization of the PNIPAM and SC concentrations as well as the addition of sodium borate achieved the selective release of (6,4) nanotubes into the liquid phase after the PNIPAM phase transition. The sorting mechanism with PNIPAM was explained by the difference in the micelle configuration on the SWCNTs and the hydrophobic collapse of PNIPAM in the presence of a sodium salt. The one-step sorting procedure for obtaining SWCNTs with a single chirality via PNIPAM will help promote their widespread application.

Optimized experimental conditions in the presence of sodium borate achieved the selective release of (6,4) nanotubes into the liquid phase.  相似文献   

5.
Hybrid anisotropic microgels were synthesised using mesoporous silica as core particles. By finely controlling the synthesis conditions, the latter can be obtained with different shapes such as platelets, primary particles or rods. Using the core particles as seeds for precipitation polymerisation, a crosslinked poly(N-isopropylacrylamide) (PNIPAM) microgel shell could be grown at the surface, conferring additional thermo-responsive properties. The different particles were characterised using scattering and imaging techniques. Small angle X-ray scattering (SAXS) was employed to identify the shape and porous organisation of the core particles and dynamic light scattering (DLS) to determine the swelling behaviour of the hybrid microgels. In addition, cryogenic transmission electron microscopy (cryo-TEM) imaging of the hybrids confirms the different morphologies as well as the presence of the microgel network and the core–shell conformation. Finally, the response of the particles to an alternating electric field is demonstrated for hybrid rod-shaped microgels in situ using confocal laser scanning microscopy (CLSM).

Hybrid anisotropic microgels with different morphologies were prepared using mesoporous silica particles as core and PNIPAM as shell. The shell thickness d and aspect ratio ρ were characterised notably via cryo-TEM (left) and DLS (right).  相似文献   

6.
At present, Antheraea pernyi silk fibroin (ASF) based hydrogels have wide potential applications as biomaterials because of their superior cytocompatibility. Herein, ASF is used as a nucleophilic reagent, reacted with allyl glycidyl ether (AGE) for the preparation of allyl silk fibroin (ASF-AGE). The investigation of ASF-AGE structure by 1H NMR and FTIR are revealed that reactive allyl groups were obtained on ASF by nucleophilic substitution. A series of ASF based hydrogels are manufactured by N-isopropylacrylamide (NIPAAm) copolymerization bridged with ASF-AGE. By the silk fibroin self-assembly process, stably physical cross-linked hydrogels are formed without any crosslinking agent. These hydrogels exhibit good thermoresponsive and degradability, for which the LCST was about 32 °C, and these hydrogels can be degraded in protease XIV solution. Excellent cell proliferation, viability and morphology is demonstrated for b End.3 cells on the hydrogels by the characteristic MTT assay, CLSM and SEM. The cytocompatibility of b End.3 cells was demonstrated with excellent cell adhesion and growth on these ASF based hydrogels in vitro. These degradable and thermoresponsive ASF based hydrogels may find potential applications for cells delivery devices and tissue engineering.

At present, Antheraea pernyi silk fibroin (ASF) based hydrogels have wide potential applications as biomaterials because of its superior cytocompatibility.  相似文献   

7.
In this study we use poly(N-isopropylacrylamide) (PNIPAM) based copolymer microgels to create free-standing, transferable, thermoresponsive membranes. The microgels are synthesized by copolymerization of NIPAM with 2-hydroxy-4-(methacryloyloxy)–benzophenone (HMABP) and spin-coated on Si wafers. After subsequent cross-linking by UV-irradiation, the formed layers easily detach from the supporting material. We obtain free standing microgel membranes with lateral extensions of several millimetres and an average layer thickness of a few hundred nanometres. They can be transferred to other substrates. As one example for potential applications we investigate the temperature dependent ion transport through the membranes via resistance measurements revealing a sharp reversible increase in resistance when the lower critical solution temperature of the copolymer microgels is reached. In addition, prior to cross-linking, the microgels can be decorated with silver nanoparticles and cross-linked afterwards. Such free-standing nanoparticle hybrid membranes are then used as catalytic systems for the reduction of 4-nitrophenol, which is monitored by UV/Vis spectroscopy.

Cross-linkable microgels are synthesized by copolymerization of NIPAM with 2-hydroxy-4-(methacryloyloxy)–benzophenone (HMABP) and are subsequently UV-cross-linked to obtain smart membranes exhibiting switchable resistance.  相似文献   

8.
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/polyhedral oligomeric silsesquioxane (PHBV/POSS) hybrids with different POSS contents of 5, 10, 15, 20, 25 and 30 wt% were prepared by solution casting. The composition, crystallization and melting behavior, crystal structure, spherulite morphology, surface morphology, and tensile properties of PHBV/POSS hybrids were characterized by EDS, DSC, FTIR, XRD, HSPOM, AFM and a tensile testing machine. The results showed that POSS was well dispersed in the PHBV matrix. PHBV and POSS crystals coexisted in the hybrids. The crystallinity of pure PHBV was larger than that of PHBV/POSS hybrids. POSS restricted the crystallization of PHBV in PHBV/POSS hybrids. With the increase of POSS content, the crystallinity of PHBV/POSS hybrids decreased from 56.8 (pure PHBV) to 33.6% (PHBV/POSS hybrid with 30 wt%). However, the introduction of POSS did not affect the spherulite morphology of PHBV. The Avrami equation was used to describe the isothermal crystallization kinetics of PHBV/POSS hybrids. The results showed that as the crystallization temperature increased, the crystallization rate became slow. In addition, POSS can improve the tensile properties of PHBV.

Polyhedral oligomeric silsesquioxane (POSS) changed the crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and improved the mechanical properties of PHBV.  相似文献   

9.
We prepared thermosensitive and biocompatible drug-loaded nanofibrous films by an electrospinning technique using a block copolymer, poly(N-isopropylacrylamide)-b-poly(l-lactide) (PNLA), and poly(l-lactide) (PLLA). The copolymer PNLA was synthesized by the radical polymerization of N-isopropylacrylamide (NIPAAm), followed by the ring-opening polymerization of l-lactide. The properties of PNIPAAm and PNLA were selectively discussed based on the results of NMR, FT-IR, GPC, and CA analyses. Because of the low molecular weight of PNIPAAm and PNLA and the hydrolysis of PNLA resulting from its hydrophilicity, these copolymers were inappropriate for electrospinning separately. Hence, a mixture of PNLA and PLLA was used to prepare electrospun nanofibrous films. SEM images of the PNLA/PLLA electrospun films showed that homogeneous fibres with smooth surfaces were obtained. In vitro release studies indicated that the drug-release rate of the PNLA/PLLA electrospun nanofibrous films can be adjusted by the content and molecular weight of PNLA and by the environmental temperature. The results demonstrate that electrospinning is a promising way to create stimuli-responsive fibrous films with potential applications in the design of controllable drug delivery systems.

Thermosensitive and biocompatible PNLA/PLLA drug-loaded nanofibrous films with different morphologies and controlled drug release behaviors by electrospinning technique.  相似文献   

10.
Some of the essential properties for cellular scaffolding are the capability to maintain the three-dimensional (3D) structure, good adhesion, and adequate elastic modulus during cell growth, migration, and proliferation. Biocompatible synthetic hydrogels are commonly used as cellular scaffolds because they can mimic the natural extracellular matrices (ECMs). However, it is possible that the physicochemical and mechanical behavior of the scaffold changes during cell proliferation and loses the scaffold properties but this is rarely monitored. In this work, the physicochemical and mechanical properties of a macroporous soft material based on poly(N-isopropyl acrylamide) (PNIPAM) have been studied during a period of 75 days at culture condition while bovine fetal fibroblasts (BFF) were grown within the matrix. The interconnected macroporous hydrogel was obtained by cryogelation at −18 °C. The swelling capacity of the scaffold was not altered during cell proliferation but changes in the mechanical properties were observed, beginning with the high elastic modulus (280 kPa) that progressively decreased until mechanical stability (40 kPa) was achieved after 20 culture days. It was observed that the matrix–cell interactions together with collagen production favor normal cellular processes such as cell morphology, adhesion, migration, and proliferation. Therefore, the observed behavior of macroporous PNIPAM as a 3D scaffold during cell growth indicates that the soft matrix is cytocompatible for a long time and preserves the suitable properties that can be applied in tissue engineering and regenerative medicine.

3D cell scaffold based on macroporous PNIPAM is cytocompatible and preserves the cell viability for more than 75 culture days.  相似文献   

11.
Aggregation and continuous π-stacking have been the major obstacles hindering the fluorescence (FL) quantum yield (ΦF) of perylene diimide (PDI) derivatives in the condensed phase. To prepare polymer microspheres with nearly unity ΦF, in this work a POSS functionalized PDI derivative, POSS–PDI–POSS (PPP), was applied as the red fluorophore of poly(3-hydroxylbutyrate-co-3-hydroxyvalerate) (PHBV) and polystyrene (PS) microspheres. The electrosprayed PPP/PHBV and PPP/PS microspheres have unique hollow structures. Moreover, they show bright red FL under a fluorescence microscope. A photophysical study of the microspheres indicates a significant role of the polymer matrix in disrupting the aggregation state and the ΦF of the embedded PPP fluorophore. Both the PPP/PHBV and the PPP/PS microspheres show higher ΦF than most PDI materials in the condensed phase. The PPP/PHBV microspheres show ΦF of 28%, whereas the PPP/PS microspheres give nearly unity ΦF.

A POSS functionalized perylene diimide (PDI) derivative, PPP, is applied to polymer microspheres as a red fluorophore. Hollow PPP/polystyrene microspheres show a fluorescence quantum yield (ΦF) of nearly unity.  相似文献   

12.
Functionalized polyhedral oligosilsesquioxanes (POSS) containing an isoxazolidine nucleus have been synthesized by microwave assisted 1,3-dipolar cycloaddition of N-methyl-C-alkoxycarbonyl nitrone 1 with POSS containing olefin moieties. The results of cycloaddition processes were rationalized by computational studies at the DFT level. The covalent conjugation of chitosan with the cycloadduct 3a leads to composite material CS-POSS 7 which was gelified using genipin as cross linking agent. The suitability of the system for bone tissue engineering purposes was evaluated by in vitro drug release studies using ketoprofen as a model drug and cytotoxicity assays performed on human fetal osteoblastic cells. The preliminary biological tests showed the lack of cytotoxicity of the hybrid material and suggest its potential role in bone tissue engineering applications.

Functionalized POSS containing an isoxazolidine nucleus have been synthesized by 1,3-dipolar cycloaddition and conjugated with chitosan for bone tissue engineering applications.  相似文献   

13.
Herein, thermo-sensitive lignocellulose hydrogels with varying lignin contents were fabricated with N-isopropylacrylamide (NIPAAm) by a semi-interpenetrating polymer network (SIPN) strategy using a LiCl/DMSO solvent system. Soda lignin mixed with the lignocellulose/LiCl/DMSO solution was also used to prepare the composite hydrogels, and the influence of the existential state of lignin on the hydrogel properties was analyzed objectively. The SIPN hydrogels exhibited more favorable mechanical properties due to the physical entanglement of poly-NIPAAm and lignocellulose. The presence of externally added lignin in the composite hydrogels is beneficial for mechanical improvement. Both the mechanical properties and the morphologies of the SIPN hydrogels can be tuned by varying the existential state and content of lignin. Furthermore, the prepared SIPN hydrogels showed rapid conversion from being hydrophilic at 20 °C to being hydrophobic at 45 °C. All SIPN hydrogels exhibited obvious oil absorbency in an oil/water mixture at 45 °C. Moreover, the different lignin existential states in the hydrogels resulted in different lower critical solution temperatures (LCST). This study provides a feasible route to produce reinforced thermo-sensitive hydrogels and develops a method for tailoring the morphology and the absorption properties of hydrogels by controlling the existential state and content of lignin.

This study provides a feasible route to produce reinforced thermo-sensitive hydrogels and tailor their morphologies and absorption properties by controlling the state and content of lignin.  相似文献   

14.
A fluorescent polymer was synthesized using N-isopropylacrylamide (NIPAM) crosslinked with a divinylazonaphthol monomer via radical emulsion polymerization. Because the crosslinked polymer contained an aggregation-induced emissive (AIE) azonaphthol-based crosslinker, a thermoreversible sol–gel transformation and gelation-induced reversible fluorescence alteration were successfully attained in an aqueous medium. Like typical PNIPAM, the size and transmittance of the polymer dramatically decreased near the lower critical solution temperature (LCST, 36 °C). Such gelation facilitated aggregation of the polymer chains, resulting in the close contact between azonaphthol groups producing fluorescence. The crosslinked polymer exhibited changes in dual properties: one is related to PNIPAM structural alteration, which corresponds to conventional swelling/shrinkage behavior; and the other is involved in the reversible fluorescence change in response to the swelling/shrinkage. Because the major backbone of the polymer was composed of NIPAM with an LCST at 36 °C, the resultant polymer is expected to have potential applications in biologically related fields.

A novel thermoresponsive polymer with AIE behavior is developed for reversible fluorescence switching using unusual AIE-active azonaphthol derivatives.  相似文献   

15.
In this study, we present a simple method to prepare and control the structure of regenerated hybrid silkworm silk films through icing. A regenerated hybrid silk (RHS) film consisting of a micro-fibrillar structure was obtained by partially dissolving amino-functionalized polyhedral oligomeric silsesquioxanes (POSS) and silk fibers in a CaCl2–formic acid solution. After immersion in water and icing, the obtained films of RHS showed polymorphic and strain-stiffening behaviors with mechanical properties that were better than those observed in dry or wet-regenerated silk. It was also found that POSS endowed the burning regenerated silk film with anti-dripping properties. The higher β-sheet content observed in the ice-regenerated hybrid micro-fibrils indicates a useful route to fabricate regenerated silk with physical and functional properties, i.e. strain-stiffening, similar to those observed to date in natural spider silk counterpart and synthetic rubbers, and anti-dripping of the flaming melt. Related carbon nanotube composites are considered for comparison.

In this study, we present a simple method to prepare and control the structure of regenerated hybrid silkworm silk films through icing.  相似文献   

16.
As an excellent model material for fundamental studies on temperature-sensitive hydrogels, poly(N-isopropylacrylamide) (NIPA) hydrogel has been applied in drug delivery, tissue engineering, and soft robotics. However, the lack of study on fracture and fatigue hinders further development of hydrogels for applications where cyclic loading–unloading is unavoidable. In this study, the fracture and fatigue damage of the NIPA hydrogel were studied for the first time by pure shear tests at different temperatures. Fracture behaviors were investigated under monotonic load from 31 °C to 39 °C. It is found that the fracture energy increases with the increase in temperature. The fracture energy is approximately 20 J m−2 near the volume phase transition temperature. Temperature also significantly influences the fatigue life. By fitting the experimental data, the fatigue limit λf is determined. The results obtained from the experimental tests would be important for the engineering applications of the NIPA hydrogels.

The fracture energy increases rapidly, when the temperature is higher than the VPTT, mainly because of the hydrophobic interactions becomes dominant.  相似文献   

17.
The development of amorphous films with a wide transmission window and high refractive index is of growing significance due to the strong demand of integrating functional nanoparticles for the next-generation hybrid optoelectronic films. High-index TeO2-based glass films made via the sol–gel process are particularly suitable as their low temperature preparation process promises high compatibility with a large variety of nanoparticles and substrates that suffer from low thermal stability. However, due to the lack of in-depth understanding of the mechanisms of the formation of undesired metallic-Te (highly absorbing species) in the films, the preparation of high-transmission TeO2-based sol–gel films has been severely hampered. Here, by gaining insight into the mechanistic chemistry of metallic-Te formation at different stages during the non-hydrolytic sol–gel process, we identify the chemical route to prevent the generation of metallic-Te in a TeO2-based film. The as-prepared TeO2-based film exhibits a high transmission that is close to the theoretical limit. This opens up a new avenue for advancing the performance of hybrid optoelectronic films via incorporating a large variety of unique nanoparticles.

This work develops a high-transparency amorphous film with a wide transmission window and high refractive index, which can potentially meet the strong demand of integrating functional nanoparticles for the next-generation hybrid optoelectronic films.  相似文献   

18.
In this study, macroporous pH-sensitive poly[N-isopropylacrylamide-co-acrylic acid-sorbitan monooleate] hydrogels, termed as PNIPAM-co-AAc-Span80 hydrogels, with an enhanced hydrophobic property and a rich pore structure were prepared by free-radical polymerization in an ethanol/water mixture. The polymerizable surfactant AAc-Span80 was obtained by the esterification of acrylic acid (AAc) and sorbitan monooleate (Span80), which was used to copolymerize with N-isopropylacrylamide (NIPAM). The chemical structure, thermal stability, morphology, and amphipathy of the PNIPAM-co-AAc-Span80 hydrogels were characterized. The results showed that the polymerizable surfactant AAc-Span80 macromolecule introduced into the hydrogels could not only increase the hydrophobic property but also ameliorate the porous network morphology, which was conducive to high adsorption capacity for adriamycin hydrochloride (DOX). The adsorption results showed that the equilibrium adsorption capacity of DOX reached 467.5 mg g−1 within 48 h at pH 7.4, and the hydrophobic interactions and intermolecular hydrogen bonds were the main force in the adsorption process of DOX. The release results demonstrated that the macroporous pH-sensitive hydrogels loaded with DOX could release 98.7% of DOX at pH 5.0, which would be highly beneficial for the release of anti-cancer drugs in the environment of cancer cells. All the results demonstrate that the PNIPAM-co-AAc-Span80 hydrogels have great potential for the delivery of anti-cancer drugs.

PNIPAM-co-AAc-Span80 shows an enhanced hydrophobic property, rich pore structure, and good adsorption performance for DOX. The desorption results demonstrate that 98.7% of DOX can be released efficiently in an acidic environment.  相似文献   

19.
Poly(methacrylic acid) (P(MAA)), poly(acrylamide) (P(AAm)) and poly(3-acrylamidopropyltrimethyl ammonium chloride) (P(APTMACl)) were synthesized as anionic, neutral and cationic hydrogels, respectively. The synthesized hydrogels have the ability to be used as absorbents for the removal of selected heavy metal ions such as Cu2+, Co2+, Ni2+ and Zn2+ from aqueous media. Absorption studies revealed that the absorption of metal ions by the hydrogels followed the order Cu2+ > Ni2+ > Co2+ > Zn2+. For the mechanism of absorption, both Freundlich and Langmuir absorption isotherms were applied. Metal ion entrapped hydrogels were treated using an in situ chemical reduction method in order to convert the metal ions into metal nanoparticles for the synthesis of hybrid hydrogels. The synthesis and morphology were confirmed using FT-IR and SEM, while the absorbed metal amounts were measured using TGA and AAS. The hybrid hydrogels were further used as catalysts for the reduction of macro (methylene blue, methyl orange and congo red) and micro (4-nitrophenol and nitrobenzene) pollutants from the aqueous environment. The catalytic performance and re-usability of the hybrid hydrogels were successfully investigated.

Poly(methacrylic acid) (P(MAA)), poly(acrylamide) (P(AAm)) and poly(3-acrylamidopropyltrimethyl ammonium chloride) (P(APTMACl)) were synthesized as anionic, neutral and cationic hydrogels respectively.  相似文献   

20.
Porous substrates composed of biodegradable polymers and nanoparticles have found extensive use as three-dimensional (3D) scaffolds to regenerate damaged tissues through the incorporation of cells or growth factors. Here, injectable thermally responsive hydrogels based on SiO2 nanoparticles (NPs), alginate, and gelatin biopolymers, with possible utilization for cartilage tissue engineering, are introduced. The nanocomposites contain different amounts of SiO2 NPs for reinforcement and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC)/N-hydroxysuccinimide (NHS) for chemical crosslinking of polymer chains in the 3D hydrogel network. The cross-sectional structure of the hydrogels containing 0.25, 1.5, and 3.0% SiO2 NPs was observed by FE-SEM, confirming porous morphology with interconnected pores. Based on the rheometer analyses, by increasing the amount of SiO2 NPs, the mechanical strength of the gels can be found. In addition, in vitro biodegradation studies show that the hydrogels without SiO2 are more unstable than the hydrogels containing SiO2 NPs. In vitro biocompatibility of the products tested by MTT assay indicates that cell viability and attachment depend on the presence of SiO2 NPs.

Thermoresponsive oxidized alginate/gelatin/SiO2 NPs injectable hydrogels have great potential in cartilage tissue engineering due to low gelation time (120 s) and body temperature gelation (37 °C).  相似文献   

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