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1.
Surfactant–polymer interactions in aqueous solutions have been studied using dynamic surface tension, polyelectrolyte titration, nephelometric turbidity, and dynamic light scattering. For the preparation of complexes, a technical cationic surfactant was used in combination with two poly(maleic acid-co-polymers) of similar structure but different hydrophobicity. The dynamic surface tensions of mixed solutions as functions of surfactant concentration at constant polyelectrolyte content, as well as changes in the surface activity due to the influence of polyanion at constant surfactant concentration are discussed in terms of a complex or aggregate formation in the bulk phase. The interaction of the surfactant with poly(maleic acid-alt-propene) (P-MS-P) and poly(maleic acid-alt--methylstyrene) (P-MS-MeSty), respectively, is strong in both cases and results in the formation of nanoparticles with properties depending on the composition of the corresponding mixture.  相似文献   

2.
Ultradispersed metal oxide nanoparticles have applications as heterogeneous catalysts for organic reactions. Their catalytic activity depends primarily on their surface area, which in turn, is dictated by their size, colloidal concentration and stability. This work presents a microemulsion approach for in situ preparation of ultradispersed copper oxide nanoparticles and discusses the effect of different microemulsion variables on their stability and highest possible time-invariant colloidal concentration (nanoparticle uptake). In addition, a model which describes the effect of the relevant variables on the nanoparticle uptake is evaluated. The preparation technique involved solubilizing CuCl(2) in single microemulsions followed by direct addition of NaOH. Upon addition of NaOH, copper hydroxide nanoparticles stabilized in the water pools formed in addition to a bulk copper hydroxide precipitate at the bottom. The copper hydroxide nanoparticles transformed with time into copper oxide. After reaching a time-independent concentration, mixing had limited effect on the nanoparticle uptake and particle size. Particle size increased with increasing the surfactant concentration, concentration of the precursor salt, and water to surfactant mol ratio; while the nanoparticle uptake increased linearly with the surfactant concentration, displayed an optimum with R and a power function with the concentration of the precursor salt. Surface areas per gram of nanoparticles were much higher than literature values. Even though lower area per gram of nanoparticles was obtained at higher uptake, higher surface area per unit volume of the reverse micellar system was attained. A model based on water uptake by Wisor type II microemulsions, and previously used to describe iron oxide nanoparticle uptake by the same microemulsions, agreed well with the experimental results.  相似文献   

3.
We have already shown that polylactide (PLA) nanoparticles covered with a hydrophilic polymeric layer can be prepared by simple emulsion/solvent evaporation by using amphiphilic copolymers as surfactants during the procedure. The external layer is then constituted by the hydrophilic part of the macromolecular surfactant. This kind of nanospheres is useful for the encapsulation of lipohilic molecules. The use of amphiphilic copolymers as surfactants in the preparation of PLA nanospheres with controlled surface properties, was then applied to the double emulsion/solvent evaporation procedure. The aim was to allow the encapsulation of water-soluble bioactive molecules in PLA particles with controlled surface properties. In this paper, we describe the results obtained with three different water-soluble monomethoxypolyethylene oxide (MPEO)-b-PLA diblock copolymers used as surfactants in the preparation of nanoparticles by double emulsion/solvent evaporation. After organic solvent evaporation, the obtained nanospheres were proved to be really covered by a MPEO layer whose characteristics were determined. It was firstly shown that the MPEO-covered particles did not flocculate at 25 degrees C, even in 4 M NaCl while suspensions of bare nanospheres were destabilized for a NaCl concentration as low as 0.04 M. On the other hand, the suspensions of MPEO-covered nanoparticles in 0.3 M Na2SO4 were found to be very sensitive to temperature as they flocculated at a temperature lying between 45 and 55 degrees C depending on the MPEO-b-PLA composition. This property was attributed to the fact that MPEO is a polymer with a low critical solution temperature. The concentration of MPEO at the nanoparticle surface was then calculated for the three kinds of particles, from the initial flocculation temperature, and was found to be comparable to the value determined directly.  相似文献   

4.
Biodegradable polymeric microspheres are ideal vehicles for controlled delivery applications of drugs, peptides and proteins. Amongst them, poly(lactic-co-glycolic acid) (PLGA) has generated enormous interest due to their favorable properties and also has been approved by FDA for drug delivery. Insulin-loaded PLGA microparticles were prepared by our developed single phase oil in oil (o/o) emulsion solvent evaporation technique. Insulin, a model protein, was successfully loaded into microparticles by changing experimental variables such as polymer molecular weight, polymer concentration, surfactant concentration and stirring speed in order to optimize process variables on drug encapsulation efficiency, release rates, size and size distribution. A 24 full factorial design was employed to evaluate systematically the combined effect of variables on responses. Scanning electron microscope (SEM) confirmed spherical shapes, smooth surface morphology and microsphere structure without aggregation. FTIR and DSC results showed drug–polymer interaction. The encapsulation efficiency of insulin was mainly influenced by surfactant concentration. Moreover, polymer concentration and polymer molecular weight affected burst release of drug and size characteristics of microspheres, respectively. It was concluded that using PLGA with higher molecular weight, high surfactant and polymer concentrations led to a more appropriate encapsulation efficiency of insulin with low burst effect and desirable release pattern.  相似文献   

5.
The interfacial behavior of silica nanoparticles in the presence of an amphiphilic polymer poly( N-isopropylacrylamide) (PNIPAM) and an anionic surfactant sodium dodecyl sulfate (SDS) is studied using neutron reflectivity. While the nanoparticles do not show any attraction to hydrophilic and hydrophobic surfaces in pure water, presence of the amphiphilic polymer induces significant adsorption of the nanoparticles at the hydrophobic surface. This interfacial behavior is activated due to interaction of the nanoparticles with PNIPAM, the amphiphilic nature of which leads to strong adsorption at a hydrophobic surface but only weak interaction with a hydrophilic surface. The presence of SDS competes with nanoparticle-PNIPAM interaction and in turn modulates the interfacial properties of the nanoparticles. These adsorption results are discussed in relation to nanoparticle organization templated by dewetting of charged polymer solutions on a solid substrate. Our previous studies showed that nanoparticle assembly can be induced to form complex morphologies produced by dewetting of the polymer solutions, such as a polygonal network and long-chain structures. This approach, however, works on a hydrophilic substrate but not on a hydrophobic substrate. These observations can be explained in part by particle-substrate interactions revealed in the present study.  相似文献   

6.
Control over nanoparticle size is a key factor which labels a given preparation technique successful. When organic reactions are mediated by ultradispersed catalysts, the concentration of the colloidal nanoparticle catalysts and their stability become key factors as well. In this study, variables affecting iron hydroxide nanoparticle size, stability, and maximum possible colloidal concentration in AOT/water/isooctane microemulsions were investigated. Iron hydroxide was prepared in single microemulsions by first solubilizing iron chloride powder in the water pools, followed by addition of aqueous NaOH. Upon addition of NaOH, Fe(OH)3 nanoparticles stabilized in the water pools formed in addition to bulk precipitate of Fe(OH)3. The time-invariant concentration of the stabilized Fe(OH)3 is defined as the nanoparticle uptake, and it corresponds to the maximum possible concentration of the colloidal nanoparticles. The effect of the following variables on the nanoparticle uptake and size distribution was investigated: mixing time; surfactant concentration; water to surfactant mole ratio; and the initial concentration of the precursor salt. At 300 rpm of mixing a constant uptake of iron hydroxide nanoparticles was achieved in about 2 h and further mixing had limited effect on the nanoparticle uptake and particle size. An optimum R was found for which a maximum nanoparticle uptake was obtained. Nanoparticle uptake increased linearly with the surfactant concentration and displayed a power function with the initial concentrations of the precursor salt. The surface area/g of the nanoparticles was much higher than literature values, however, following a trend opposite to that of the nanoparticle uptake. The surface area/unit volume of the microemulsion, on the other hand, followed the same trend as the nanoparticle uptake. The particle size increased as R and/or the surfactant concentration increased. A mathematical model based on correlations for water uptake by Winsor type II microemulsions accurately accounted for the effect of the aforementioned variables on the nanoparticle uptake.  相似文献   

7.
The polar orientation and degree of conformational order of sodium dodecyl sulfate (SDS) adsorbed at the hydrophobic octadecanethiol/aqueous solution interface in the presence of poly(ethylene glycol) (PEG) has been investigated as a function of the surfactant concentration and the molecular weight of the polymer. Sum frequency generation (SFG) vibrational spectroscopy was employed to obtain spectra of interfacial surfactant; weak SFG signals from interfacial polymer were also detected for polymer molecular weights of 900 and above. The phase of the SFG spectra indicated that both the surfactant and polymer had a net orientation of their CH2 and/or CH3 groups toward the hydrophobic surface. Spectra of SDS in the presence of mixed polymer/surfactant solutions showed increasing conformational order as the surfactant concentration was raised. At the lowest surfactant concentrations, the spectra of SDS were weaker in the presence of the polymer than in its absence. All PEG molecular weights investigated, with the exception of PEG 400, gave rise to significant inhibition of ordered surfactant adsorption below the critical micelle concentration. The greatest inhibitory effect was noted for PEG 900. Probing interfacial PEG specifically through the use of perdeuterated SDS revealed that the polymer spectral intensity decreased monotonically as the surfactant concentration was increased for all polymer molecular weights where a PEG spectrum was apparent. These findings are interpreted in terms of the displacement of preadsorbed polymer as the surfactant concentration increases. This result is compatible with observations of adsorption from SDS/PEG solutions at solid/solution and solution/air interfaces made using other techniques.  相似文献   

8.
A novel method of preparing AgCl nanoparticles by mixing AgCl powder and a microemulsion consisting of dioctyldimethylammonium chloride/n-decanol/water/isooctane is introduced. This new method was discovered during the preparation of AgCl nanoparticles in single microemulsions by direct reaction with the dioctyldimethylammonium chloride surfactant counterion. The effect of the following variables on the concentration of the colloidal AgCl nanoparticles (the nanoparticle uptake) and the particle size were studied: (1) operating variables, including mixing and temperature; and (2) microemulsion variables, including surfactant and cosurfactant concentration, and water to surfactant mole ratio. Manipulating these variables provides an insight into the role of the surfactant surface layer rigidity on the phenomenon. The results were explained by the effect of these variables on reaction rates and the colloidal nanoparticle stability. Mixing had a significant effect on the nanoparticle uptake. At 300 rpm an equilibrium AgCl nanoparticle uptake was achieved in about 1 h, while without mixing only 5% of the equilibrium value was reached even after 24 h. An optimum temperature was found for which a maximum nanoparticle uptake was obtained. At higher temperatures, the nanoparticle uptake declined. The nanoparticle uptake increased linearly with the surfactant concentration, and the particle size increased as well. A monotonic decrease in the nanoparticle uptake accompanied by an increase in the particle size was observed when increasing n-decanol concentration or the water to surfactant mole ratio.  相似文献   

9.
The nanoparticles of chitosan (CS) were prepared using pentasodium triphosphate (TPP) as a crosslinking agent and the influences of cetyltrimethylammonium bromide (CTAB) on the physicochemical properties of the CS-TPP nanoparticles were first studied by laser light scattering, zeta potential, and transmission electron microscopy (TEM). The concentration played a significant role in controlling the particle size of CS and the overlap concentration c(*) was testified to be about 1.0 mg/mL. The combination of static light scattering (SLS) and dynamic light scattering (DLS) allowed us to obtain more information about the CS-TPP nanoparticles in the presence of surfactant molecules. The addition of CTAB could reduce the hydrodynamic diameter of nanoparticles effectively in the salt solutions and simultaneously increase the zeta potential of the nanoparticles. The effect of CTAB concentration on the size of CS-TPP nanoparticle was also examined. The critical micelle concentration (CMC) of CTAB was used to interpret the complicated complex formed by the polyelectrolyte and the surfactant. Finally, TEM was used to observe the CS-TPP nanoparticles, which were affected by CTAB, to verify the results obtained by light scattering.  相似文献   

10.
The wetting properties of surfactants on solid surfaces form the basis of many industrial and biological processes. The preferential adsorption of the surfactants from aqueous solutions onto solid surfaces alter the adhesion tension of the surface and this behavior may cause partial to complete wetting of the surfaces by the aqueous surfactant solutions. However, different types of surfactants show different wetting characteristics. To study the wetting properties of biologically produced rhamnolipids (RL), advancing contact angles of the aqueous solutions of the RL mixture of R1 and R2 in a ratio of R2/R1=1.1 were measured as a function of surfactant concentration. For a comparison of the wetting performance, sodium dodecyl sulfate (SDS) was chosen as the reference surfactant. A hydrophilic glass surface, a hydrophobic polymer, polyethylene terephthalate (PET), and gold surface were used as the solid surfaces to determine the wetting characteristics of rhamnolipids. At low surfactant concentrations (RL concentration <3x10(-5)M, SDS concentration<3x10(-4)M) contact angle (Theta) varied in a certain range depending on the character of the surfactant interactions with the surface. This was followed by a decrease in contact angle. Parallel to this behavior, at low surfactant concentrations the adhesion tension decreased, then remained constant and an increase at higher surfactant concentrations was obtained on hydrophobic surfaces. On hydrophilic surfaces a steady decrease in adhesion tension was observed with both surfactant solutions.  相似文献   

11.
The effect of ethanol on the interaction between the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic polymer poly(vinylpyrrolidone) (PVP) has been investigated using a range of techniques including surface tension, fluorescence, electron paramagnetic resonance (EPR), small-angle neutron scattering (SANS), and viscosity. Surface tension and fluorescence studies show that the critical micelle concentration (cmc) of the surfactant decreases to a minimum value around 15 wt % ethanol; that is, it follows the cosurfactant effect. However, in the presence of PVP, the onset of the interaction, denoted cmc(1), between the surfactant and the polymer is considerably less dependent on ethanol concentration. The saturation point, cmc(2), however, reflects the behavior of the cmc in that it decreases upon addition of ethanol. This results in a decrease in the amount of surfactant bound to the polymer [C(bound) = cmc(2) - cmc] at saturation. The viscosity of simple PVP solutions depends on ethanol concentration, but since SANS studies show that ethanol has no effect on the polymer conformation, the changes observed in the viscosity reflect the viscosity of the background solvent. There are significant increases in bulk viscosity when the surfactant is added, and these have been correlated with the polymer conformation extracted from an analysis of the SANS data and with the amount of polymer adsorbed at the micelle surface. Competition between ethanol and PVP to occupy the surfactant headgroup region exists; at low ethanol concentration, the PVP displaces the ethanol and the PVP/SDS complex resembles that formed in the absence of the ethanol. At higher ethanol contents, the polymer does not bind to the ethanol-rich micelle surface.  相似文献   

12.
采用改进的Polyol合成法,以PEO-PPO-PEO为表面活性剂制备了链霉亲和素-异硫氰酸荧光素偶联的Fe3O4/Au纳米粒子;利用透射电镜和X射线衍射仪分析证实了Fe3O4/Au的核壳型纳米结构,确定了其粒径和分布;采用紫外-可见吸收光谱仪和荧光光谱仪测定了所制备的纳米粒子的光学活性和荧光特性,并采用振动样品磁强计(VSM)测量了其磁化率.结果表明,所制备的Fe3O4/Au纳米粒子具有光学活性和荧光特性,以及优异的磁性.  相似文献   

13.
W dispersed mixed polymers of ethylene propylene monomer and high density polyethylene were prepared by means of a twin-screw extruder by the conventional technique using a co-rotated two-roll mill. The W nanoparticles used as filler were prepared by pulse wire evaporation then coated with low-density polyethylene (LDPE) as polymeric surfactant. Surface treatment of the nanoparticles with LDPE was conducted to enhance the wettability and lubrication of the fillers in the polymer matrix. According to SEM images and mechanical properties, dispersion of W/LDPE nanoparticles in the polymer matrix was homogeneous, and adhesion of the nanoparticles to the matrix was strong. The polymer nanocomposites had better mechanical properties than those containing dispersed micro-W powder. The γ-ray attenuation factor of nanofiller-reinforced composites was substantially enhanced compared with that containing micro filler.  相似文献   

14.
The dynamic adsorption behavior of mixtures of the cationic polymer poly(dimethyldiallylammonium chloride) [poly(dmdaac)] and the anionic surfactant sodium dodecyl sulfate (SDS) has been studied at the expanding liquid surface of an overflowing cylinder. A combination of ellipsometry and external reflection Fourier transform infrared spectroscopy was used to measure the adsorbed amounts of poly(dmdaac) and SDS as a function of the bulk surfactant concentration for various polymer concentrations in the range 0-0.2 g dm-3. Laser Doppler velocimetry was used to determine the surface age, which was approximately 1 s for solutions where the polymer adsorbed. The interfacial behavior is rationalized in terms of competition between surface activity and mass transport to the expanding surface. At low surfactant concentrations, adsorption of both poly(dmdaac) and SDS is enhanced as a result of the formation in solution of polymer-surfactant complexes that are more surface active than either component alone. The rate of adsorption of these complexes is diffusion-controlled, and their interfacial composition remains constant at three dmdaac units per SDS molecule over a 5-fold change in the surfactant concentration. For the higher polymer concentrations studied, the complexes saturate the air-water interface: the adsorbed amount is independent of the polymer concentration and remains constant also over a factor of 5 in the surfactant concentration. Once the number of bound surfactant molecules per dmdaac monomer exceeds 0.3, the complexes begin to form large aggregates, which are not surface active due to their slower mass transport. The adsorbed amount decreases rapidly on approach to the equivalence point (one SDS molecule per dmdaac monomer), and when it is reached, only a very small amount of material remains at the interface. At still higher surfactant concentrations, the free SDS adsorbs but there is no adsorbed poly(dmdaac). The dynamic adsorption data are compared with equilibrium measurements of the same system by Staples et al. (Langmuir 2002, 18, 5147), which show very different surface compositions and no significant change in surface coverage at the equivalence point.  相似文献   

15.
聚乙烯吡咯烷酮包裹核壳型Fe_3O_4/Au纳米粒子的制备   总被引:1,自引:1,他引:0  
采用改进的Polyol合成法,以聚乙烯吡咯烷酮(PVP)为表面活性剂制备PVP包裹的单分散的Fe3O4/Au纳米粒子.透射电镜(TEM)和X射线衍射(XRD)分析证实了Fe3O4/Au的核壳型纳米结构,并确定了纳米粒子的尺寸大小和分布.UV-Vis测定显示了所制备的纳米粒子具有光学活性,而振动样品磁强计(VSM)测量显示纳米粒子具有优异的磁化率.  相似文献   

16.
表面活性剂与高分子链混合体系的模拟   总被引:3,自引:0,他引:3  
计算机模拟了高分子链对表面活性剂胶束形成过程的影响,以及高分子链构象性质随胶束化过程的变化.结果表明,当高分子链与表面活性剂之间的相互作用强度超过临界值后,高分子链的存在有利于表面活性剂胶束的形成.临界聚集浓度(CAC)与临界胶束浓度(CMC)的比值CAC/CMC随高分子链长的增大和相互吸引作用的增强而减小.在CAC之前,高分子链与表面活性剂分子只有动态的聚集;但在CAC之后,表面活性剂胶束随表面活性剂浓度X的增加而增大,并静态地吸附在高分子链上,形成表面活性剂/高分子聚集体.随着表面活性剂分子的加入,高分子链的均方末端距和平均非球形因子先保持恒定;从X略小于CAC开始, 和快速减小,至极小值后又逐渐增大.模拟结果支持高分子链包裹在胶束表面的实验模型.  相似文献   

17.
The dynamic adsorption of polymer/surfactant mixtures containing poly(ethylene oxide) (PEO) with either tetradecyltrimethylammonium bromide (C(14)TAB) or sodium dodecyl sulfate (SDS) has been studied at the expanding air/water interface created by an overflowing cylinder, which has a surface age of 0.1-1 s. The composition of the adsorption layer is obtained by a new approach that co-models data obtained from ellipsometry and only one isotopic contrast from neutron reflectometry (NR) without the need for any deuterated polymer. The precision and accuracy of the polymer surface excess obtained matches the levels achieved from NR measurements of different isotopic contrasts involving deuterated polymer, and requires much less neutron beamtime. The PEO concentration was fixed at 100 ppm and the electrolyte concentration at 0.1 M while the surfactant concentration was varied over three orders of magnitude. For both systems, at low bulk surfactant concentrations, adsorption of the polymer is diffusion-controlled while surfactant adsorption is under mixed kinetic/diffusion control. Adsorption of PEO is inhibited once the surfactant coverage exceeds 2 μmol m(-2). For PEO/C(14)TAB, polymer adsorption drops abruptly to zero over a narrow range of surfactant concentration. For PEO/SDS, inhibition of polymer adsorption is much more gradual, and a small amount remains adsorbed even at bulk surfactant concentrations above the cmc. The difference in behavior of the two mixtures is ascribed to favorable interactions between the PEO and SDS in the bulk solution and at the surface.  相似文献   

18.
The effect of a low molecular weight nonionic surfactant and an acrylic associative thickener on the rheology of polyacrylamide in aqueous glycerol solutions under steady shear was experimentally investigated. The nonionic surfactant (Tween20), associative thickener (Acrysol TT935) and polyacrylamide (Separan AP30) underwent complex molecular interactions in solution as reflected by rheological measurements. The surfactant also interacted with the glycerol solvent. The addition of surfactant in aqueous glycerol solutions reduced the surface tension, as well as the solution viscosity, at low surfactant concentration. The solution viscosity went through a minimum at certain surfactant concentration, depending on the composition of glycerol/water mixture, before increasing again. Similar behavior was found when the surfactant was added to the polyacrylamide solution, except there was an initial increase in the viscosity before the reduction. The associative thickener, Acrysol TT935 (an anionic acrylic emulsion copolymer) exhibited a strong affinity with polyacrylamide in solution, as indicated by a sharp increase in the solution viscosity. The dilute polyacrylamide solution became highly elastic in the presence of either the nonionic surfactant on the associative thickener. A threestage model was proposed to describe the surfactant/thickener/polymer interactions.  相似文献   

19.
Water-in-oil, high internal phase emulsion made of super-cooled aqueous solution containing a mixture of inorganic salts and stabilized with non-ionic surfactant (sorbitan monooleate) alone was investigated. It was not possible to produce a highly concentrated emulsion (with aqueous phase fraction = 94 wt %), stabilized with surface-treated silica, solely: we were able to form an emulsion with a maximal aqueous phase mass fraction of 85 wt % (emulsion inverts/breaks above this concentration). The inversion point is dependent on the silica particle concentration, presence of salt in the aqueous phase, and does not depend on the pH of the dispersed phase. All emulsions stabilized by the nanoparticles solely were unstable to shear. So, the rheological properties and stability of the emulsions containing super-cooled dispersed phase, with regards to crystallization, were determined for an emulsion stabilized by non-ionic surfactant only. The results were compared to the properties obtained for emulsions stabilized by surface treated (relatively hydrophobic) silica nanoparticles as a co-surfactant to sorbitan monooleate. The influence of the particle concentration, type of silica surface treatment, particle/surfactant ratio on emulsification and emulsion rheological properties was studied. The presence of the particles as a co-stabilizer increases the stability of all emulsions. Also, it was found that the particle/surfactant ratio is important since the most stable emulsions are those where particles dominate over the surfactant, when the surfactant’s role is to create bridging flocculation of the particles. The combination of the two types of hydrophobic silica particles as co-surfactants is: one that resides at the water/oil interface and provides a steric boundary and another that remains in the oil phase creating a 3D-network throughout the oil phase, which is even more beneficiary in terms of the emulsion stability.  相似文献   

20.
A series of structurally well-defined poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers that undergo surface induced self assembly on hydrophobic biomaterial surfaces were synthesized and characterized. The surfactant polymers consist of low molecular weight (Mw) chitosan backbone with hydrophilic poly(ethylene oxide) (PEO) and hydrophobic hexyl pendant groups. Chitosan was depolymerized by nitrous acid deaminative cleavage. Hexanal and aldehyde-terminated PEO chains were simultaneously attached to low Mw chitosan hydrochloride via reductive amination. The surfactant polymers were prepared with various ratios of the two side chains. The molecular composition of the surfactant polymers was determined by FT-IR and 1H NMR. Surface active properties at the air–water interface were determined by Langmuir film balance measurements. The surfactant polymers with PEO/hexyl ratios of 1:3.0 and 1:14.4 were used as surface modifying agents to investigate their anti-infection properties. E. coli adhesion on Silastic® surface was decreased significantly by the surfactant polymer with PEO/hexyl 1:3.0. Surface growth of adherent E. coli was effectively suppressed by both tested surfactant polymers.  相似文献   

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