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1.
Macroporous poly(N‐isopropylacrylamide) (PNIPA) hydrogels were synthesized by free‐radical crosslinking polymerization in aqueous solution from N‐isopropylacrylamide monomer and N,N‐methylenebis (acrylamide) crosslinker using poly(ethylene glycol) (PEG) with three different number‐average molecular weights of 300, 600 and 1000 g mol?1 as the pore‐forming agent. The influence of the molecular weight and amount of PEG pore‐forming agent on the swelling ratio and network parameters such as polymer–solvent interaction parameter (χ) and crosslinking density (νE) of the hydrogels is reported and discussed. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying different molecular weights and compositions of PEG during polymerization. At a temperature below the volume phase transition temperature, the macroporous hydrogels absorbed larger amounts of water compared to that of conventional PNIPA hydrogels, and showed higher equilibrated swelling ratios in aqueous medium. Particularly, the unique macroporous structure provides numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to external temperature changes during the swelling and deswelling process. These macroporous PNIPA hydrogels may be useful for potential applications in controlled release of macromolecular active agents. Copyright © 2006 Society of Chemical Industry  相似文献   

2.
Low‐density unsaturated polyester resin (LDUPR) is an extended application of unsaturated polyester resin (UPR) material. In this study, azodiisobutyronitrile (AIBN) and azobisisoheptonitrile (ABVN) were presented as composite foaming agents and as initiators in LDUPR manufacturing. On the basis of the kinetics of AIBN and ABVN, their optimum half‐lives (t1/2's) for LDUPR were both 1.0 h. In this study, the mass ratio of AIBN and ABVN was chosen at 7:3, and the preferred amount of the composite foaming agent was 2 wt % resin. They were treated at a molding temperature of 78.7 ± 1.0°C. The obtained LDUPR had an apparent density of 0.37 ± 0.01 g/cm3 and a specific compression strength of 35.58 ± 1.50 MPa·g?1·cm?3; it approached the highest specific compression strength value of rigid polyurethane foam (28–35 MPa g?1 cm?3). A dual‐initiation and dual‐foaming mechanism based on the dual‐exothermic decomposition properties of the composite foaming agent was proposed with the support of the differential scanning calorimetry and scanning electron microscopy results. In the first stage, ABVN decomposed, released bubble nuclei, and initiated UPR cross‐polymerization. The bubble nuclei spread in the resin glue and grew. In the second stage, the gas in resin glue was enriched by the AIBN decomposition. The gelation time of the resin glue was influenced by AIBN and delayed. With the curing of resin, more bubbles grew up, took shape, and were retained in the UPR matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40238.  相似文献   

3.
A series of pH‐sensitive semi‐IPN hydrogels, composed of varying amounts of monomer acrylic acid(AAc), crosslinker N,N′ methylene bisacrylamide, polymer cellulose acetate (CA) were synthesized via photoinitiated polymerization in dimethyl formamide (DMF) medium. The CA/P (AAc) hydrogels were characterized by FTIR, and TG analysis. The equilibrium water uptake data was used to determine various network parameters. For all the samples synthesized, the swelling exponent “n,” initial diffusion coefficient D and average diffusion coefficient Dave were found to be in the range of 0.51–0.72, 3.16 to 7.14 × 10?6 cm2 min?1 and 94.16–120.56 cm2 min?1, respectively. The hydrogel demonstrated fair pH‐dependent swelling behavior, with nearly 20% swelling in the medium of pH 1.0 and 615% in the medium of pH 7.4 at 37°C, respectively. The gel showed excellent swelling–deswelling cycles which were interpreted quantitatively by first order kinetic swelling and deswelling models. Finally, the preliminary insulin release study, carried out in the media of varying pH, observed almost 16% release of entrapped drug in the simulating gastric fluid (SGF) of pH 1.0 in first 2 h and nearly 51% in next 6 h in simulating intestinal fluid(SIF) of pH 7.4 at 37°C. POLYM. ENG. SCI., 53:2129–2140, 2013. © 2013 Society of Plastics Engineers  相似文献   

4.
This study reports the low‐temperature and clean fabrication of porous poly(lactic acid) (PLA) through solid‐state foaming using various mixtures of ethyl lactate (EL) and supercritical CO2 (scCO2) as the blowing agent. Results showed that adding a small amount of EL (up to 0.2% molar fraction) to scCO2 enhanced the plasticizing effect of the blowing agent mixture. As a direct consequence, at an operating temperature of 35 °C, PLA foams could be manufactured with homogeneous morphology, density as low as 0.09 ± 0.01 g cm?3, mean pore sizes up to 519.0 ± 205.0 µm and pore densities in the range 2.0 × 105 to 3.4 × 108 pores cm?3. Conversely, at a temperature of 40 °C, an increase of plasticizer concentration in the blowing agent mixture up to 0.2% promoted the crystallization of the polymer during sorption stage and, consequently, foaming was slightly reduced. © 2013 Society of Chemical Industry  相似文献   

5.
Hydrogels are synthesized from methyl methacrylate (MMA) and N-vinyl-2-pyrrolidone (NVP) with 1,1,1-trimethylol propane trimethacrylate (TPTA) as a crosslinking agent. It was polymerized under UV radiation (365nm) with a small amount of photosensitizer, diethoxy acetophenone (DEAP), acclerator and diluent, triethanol amine (TEA). The hydrogels were characterized by measuring the water retention, dissolved oxygen diffusivity and permeability, mechanical strength, and light transparency. The hydrogels can retain water up to 80 wt.-% and the mechanical strenght is weakened as the water content is increased in the gel. The dissolved oxygen diffusivity and permeability in the swelling hydrogels are determined to be 10?6 cm2/sec and 1013 cm2s?1 Pa?1, respectively. The light transparency is over 90% in the wave lenght ranging from 500 to 700 nm.  相似文献   

6.
Swelling and adsorption properties of poly(hydroxamic acid), (PHA) hydrogels in aqueous solutions of some phenazine dyes such as Neutral Red, Safranin T, and Janus Green have been investigated. PHA hydrogels containing N,N′ methylenebisacrylamide or ethyleneglycoldimethacrylate were used in experiments on swelling, diffusion and adsorption of the dyes. The equilibrium swelling (Seq) values of PHA hydrogels in aqueous solutions of the phenazine dyes were calculated as 2.16–33.25 g g?1. Swelling kinetic parameters such as initial swelling rate, swelling rate constant, and maximum swelling were found. Dye diffusion into hydrogels was found to be non‐Fickian in character. Diffusion coefficients are ranged 1.32 × 10?6 cm2 s?1 ? 44.70 × 10?6 cm2 s?1. Adsorption of the phenazine dyes onto PHA hydrogels was studied by batch technique. PHA hydrogels in the phenazine dye solutions showed the dark coloration. The data was found that Freundlich isotherm model fits. According the Freundlich constants, the adsorption isotherms are of S‐type in Giles classification. All swelling and binding parameters for PHA‐EGDMA were found to be higher than those for PHA‐NNMBA. The type of crosslinker influenced the swelling, binding, and sorption more than the type of dye. Finally, it can be said that PHA hydrogels may be used a sorbent for removal of dyes. POLYM. ENG. SCI., 58:310–318, 2018. © 2017 Society of Plastics Engineers  相似文献   

7.
Highly swollen acrylamide (AAm)/sodium acrylate (SA) hydrogels were prepared by free radical solution polymerization in aqueous solution of AAm with SA as comonomer and two multifunctional crosslinkers such as glutaraldehyde (GL) and divinylbenzene (DVB). Water absorption and percentage swelling were determined gravimetrically. The influence of SA content in hydrogels was examined. Percentage swelling ratio of AAm/SA hydrogels was increased up to 2946–12,533%, while AAm hydrogels swelled up to 1326–1618%. The values of equilibrium water content of the hydrogels are between 0.9297–0.9921. Diffusion behavior was investigated. Water diffusion into hydrogels was found to be non‐Fickian in character. Adsorption properties of AAm/SA hydrogels in aqueous thionin solution have been investigated. Finally, the amount of sorbed thionin per gram of dry hydrogel (qe) was calculated to be 4.81 × 10?6?11.69 × 10?6 mol thionin per gram for hydrogels. Removal efficiency (RE%) of the AAm/SA hydrogels was changed range 37.03–68.82%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

8.
A novel practical strategy for preparing highly porous superabsorbent hydrogels (HPSHs) was invented. HPSHs were quantitatively prepared through an optimized rapid convenient solution polymerization of partially neutralized acrylic acid in the presence of a crosslinking agent under normal atmospheric conditions. Acetone and sodium bicarbonate were used as porosity generators (porogens) during the polymerization process to create highly porous structures. Time and sequence of addition of the porogens, as well as the gelation time of the polymerization, were recognized to affect the efficiency of the porogens. Sodium bicarbonate produced the more porous hydrogels with a higher rate of swelling. In comparison with a hydrogel prepared under porogen‐free conditions (control), acetone and sodium bicarbonate enhanced the swelling rate as high as 43–55% and 111–131% of the control, respectively. When both the porogens were used consecutively in the process, a remarkable synergistic effect was observed in the swelling rate of the products. Nearly all the two‐porogen processes resulted in foamy products from the polymerization system. With the single‐porogen systems, however, the foam formation stage was observed only in a part of the total process time. The apparent volume of the as‐synthesized foamy products prepared from the two‐porogen system was more than that of the single‐porogen systems by up to fourfolds. Morphological studies using scanning electron microscopy (SEM) showed that the two‐porogen systems created highly porous structures. The density of all the HPSHs synthesized was about 1.5 g cm?3 and no distinct differences were observed in their equilibrium swelling. These superabsorbent hydrogels exhibited a very high rate of swelling, so that their swelling time was measured to be less than one minute. Copyright © 2003 Society of Chemical Industry  相似文献   

9.
Intercalated and exfoliated polystyrene/nano‐clay composites were prepared by mechanical blending and in situ polymerization respectively. The composites were then foamed by using CO2 as the foaming agent in an extrusion foaming process. The resulting foam structure is compared with that of pure polystyrene and polystyrene/talc composite. At a screw rotation speed of 10 rpm and a die temperature of 200°C, the addition of a small amount (i.e., 5 wt%) of intercalated nano‐clay greatly reduces cell size from 25.3 to 11.1 μm and increases cell density from 2.7 × 107 to 2.8 × 108 cells/cm3. Once exfoliated, the nanocomposite exhibits the highest cell density (1.5 × 109 cells/cm3) and smallest cell size (4.9 μm) at the same particle concentration. Compared with polystyrene foams, the nanocomposite foams exhibit higher tensile modulus, improved fire retardance, and better barrier property. Combining nanocomposites and the extrusion foaming process provides a new technique for the design and control of cell structure in microcellular foams.  相似文献   

10.
The rate of swelling is one of the most important parameters of hydrogel polymeric networks; therefore, the objective of this study was to develop a new method to synthesize superporous poly(acrylic acid-co-acrylamide) hydrogels to improve swelling rate. The hydrogel was prepared in the presence of a foaming agent (comprising azodicarbonamide and zinc oxide), using 2,2′-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride as the initiator. The N2 released during the polymerization led to the formation of a slightly foamed gel; we refer to the process as a prefoaming process. The obtained gel underwent a further foaming process to form a superporous hydrogel. Unlike in existing methods, the consistent time control of the foaming agent addition and the onset of gelling were not necessary in this simplified gel preparation procedure. The water absorbent behavior of the superporous hydrogels suggested that the polymers obtained from the prefoaming process reached the swelling equilibrium more rapidly than those with little prefoaming, and their absorbent capacity was greater. Scanning electron microscope images show that interconnected pores inside these superporous gels formed capillary channels, which are critical for the fast swelling rate. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

11.
Poly[(diethylaminoethyl methacrylate)‐graft‐(ethylene glycol)] hydrogels were prepared with a molar ratio of 10:1 of diethylaminoethyl methacrylate to poly(ethylene glycol) of number‐average molecular weights (Mn) 200, 400 and 1000 g mol?1 using tetra(ethylene glycol) dimethacrylate to give a crosslinking ratio between 0.5 and 4.0 %. Glucose oxidase and catalase were immobilized in the matrix during polymerization. The maximum enzyme loading used was 6.6 × 10?4 g of glucose oxidase per g of polymer. The equilibrium and dynamic swelling properties of these hydrogels were investigated. The pH‐dependent equilibrium swelling characteristics showed a sharp transition between the swollen and the collapsed state at pH 7.0. The dynamic response of the hydrogel discs to pH was analyzed in pulsatile pH conditions. The effects of particle size, crosslinking and molecular weight of poly(ethylene glycol) (PEG) on the dynamic swelling response were investigated. The pulsatile nature of the response was analyzed using Boltzmann superposition. Swelling–pH master curves were obtained. Copyright © 2004 Society of Chemical Industry  相似文献   

12.
Hydrogels with semi‐interpenetrating networks composed of poly(acrylic acid) (PAAc) and poly(aspartic acid) (PASP) have great potential for pharmaceutical and biomedical applications. In this study, we aimed to synthesize semi‐interpenetrating PAAc/PASP hydrogels with improved swelling–deswelling properties via two‐step polymerization, in which the first step of polymerization was performed at 37 °C for 15 min and the second step, the freezing polymerization, was performed at ?20 °C for 24 h. The synthesized hydrogels were characterized with field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The swelling and deswelling behaviors of the hydrogels in response to the ionic strength of the buffer solution were investigated. The Schott's swelling kinetic model was used to elucidate the swelling behavior of the hydrogels. The swelling and deswelling rates of the hydrogels prepared via freezing polymerization were faster than those of the hydrogels prepared via conventional polymerization. This was attributed to the large mean pore size of the freeze‐polymerized hydrogels. The PAAc/PASP hydrogels that underwent freezing polymerization had better swelling–deswelling characteristics than the PAAc hydrogels. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43515.  相似文献   

13.
Extraction or concentration with temperature‐sensitive hydrogels is a novel separation technology. In this study, N‐isopropylacrylamide (NIPA) was synthesized by acrylonitrile and isopropanol. Poly(N‐isopropylacrylamide) (PNIPA) and copolymer of NIPA and 2‐acrylamide‐2‐methylpropane sulfonate [P(NIPA‐co‐AMPS)] hydrogels were prepared by radiation polymerization. Dependence of their swelling behavior on temperature was studied. Effects of radiation dose on polymerization, feed composition on thermoresponse, electrolyte on relative swelling ratio, and swelling and deswelling kinetics were investigated. The experimental results showed that P(NIPA‐co‐AMPS) hydrogels with low content of AMPS/NIPA (1–5 %), prepared at a radiation dose‐rate of 1 kGy/h and total dose of 30–40 kGy, could enhance the swelling ratio of PNIPA hydrogels significantly and raise the phase‐transition temperatures. P(NIPA‐co‐AMPS) hydrogels produced under optimum conditions were used to concentrate aqueous bovine serum albumin (BSA, M = 69 000 g mol?1) solution. When aqueous BSA concentration was below 5 %, the separation efficiency was more than 80 % with low cost and low energy consumption. Copyright © 2005 Society of Chemical Industry  相似文献   

14.
A series of phthalonitrile end-capped sulfonated polyarylene ether nitriles are synthesized via K2CO3 mediated nucleophilic aromatic substitution reaction at various molar ratios. The as-prepared polymer structures are confirmed by 1H NMR and FTIR spectroscopy. The properties of membranes cast from the corresponding polymers are investigated with respect to their structures. The membranes exhibit good thermal and mechanical properties, low methanol permeability (0.01?×?10?6–0.58?×?10?6 cm2·s?1 at 20 °C), and high proton conductivity (0.021–0.088 S·cm?1 at 20 °C). The introduction of phthalonitrile is proved to increase intermolecular interaction, mainly contributing to the reduction in water uptake, swelling ratio, and methanol permeability. More importantly, its introduction does not decrease the proton conductivity, but there is a slight increase. Furthermore, the selectivity of SPEN-CN-50 can reach 4.11?×?105 S·s·cm?3, which is about nine times higher than that of Nafion 117. All the data show that the as-prepared membranes may be potential proton exchange membrane for DMFCs applications.  相似文献   

15.
Poly(HEMA‐MAA) hydrogel particles were synthesized by redox free‐radical polymerization using 2‐hydroxyethylmethacrylate, different concentration of methacrylic acid as monomer, ethyleneglycol dimethacrylate as crosslinking agent, and APS/TEMED as free‐radical initiator. Fourier transform infrared spectrum of poly(HEMA‐MAA) hydrogels showed intense absorption peak of carbonyl group at ~ 1700 cm?1 due to carboxylic acid groups of MAA, peak at ~ 2960 cm?1 due to CH stretching and vinylic peak at 1700 cm?1 independent of MAA concentration. Highest swelling percentage 587% was observed in case of poly(HEMA‐MAA) hydrogel synthesized using 30% of MAA while lowest swelling percentage 413% was observed in hydrogel synthesized 10% of MAA at basic pH (8.0). Scanning electron micrograph of copolymeric particles showed the irregular shape of poly(HEMA‐MAA) particles with conglomeration with each due to ionization of carboxylic groups. Insulin was radiolabeled using technetium‐99m radionuclide and the radiolabeling efficiency was found to be 99%. Poly(HEMA‐MAA) hydrogel having 60% of MAA showed the highest insulin loading efficiency of 68% while lowest 37% was observed in case of 10% MAA hydrogel. Insulin release studies showed only 35–65% of insulin was released into the medium from particles at pH 2.5 in 60 min, while insulin release was significantly higher at pH 7.4. Hypoglycemic effect of the 60 and 80 I.U./kg insulin dose loaded in poly(HEMA‐MAA) copolymeric particles were carried out in fasted diabetic rats and highest decrease in blood glucose level from 506 mg/dL to 170 mg/dL was observed within first 3 h. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.  相似文献   

16.
Temperature‐sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] [P(DEAEMA‐co‐DMAAm)] hydrogels with five different DMAAm contents were synthesized with and without the addition of sodium carbonate as porosity generator. The synthesized hydrogels were characterized with dry gel density measurements, scanning electron microscopy observation and the determination of swelling ratio. The influence of the pore‐forming agent and content of DMAAm on swelling ratio and network parameters such as polymer–solvent interaction parameter (χ), average molecular mass between crosslinks (M?c) and mesh size (ζ) of the cryogels are reported and discussed. The swelling and deswelling rates of the porous hydrogels are much faster than for the same type of hydrogels prepared via conventional methods. At a temperature below the volume phase transition temperature, the macroporous hydrogels also absorbed larger amounts water compared to that of conventional hydrogels and showed obviously higher equilibrated swelling ratios in aqueous medium. In particular, the unique macroporous structure provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to the external temperature changes during the deswelling and swelling processes. These properties are attributed to the macroporous and regularly arranged network of the porous hydrogels. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying porosity generation methods during the polymerization reaction. Copyright © 2007 Society of Chemical Industry  相似文献   

17.
Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF3· Et2O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and1H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (Tg), the DSC data imply that the resulting copolymers have a lower Tg than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10?5 S cm?1 at room temperature and 2.79 × 10?4 S cm?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry  相似文献   

18.
In this article, we report a novel physical and chemical composite foaming system, which was used to successfully prepare high‐performance and low‐cost composite superabsorbent [poly(sodium acrylic acid) (PAA–Na)] hydrogels based on acrylic acid by free‐radical polymerization in a water bath under a nitrogen atmosphere without the use of any organic solvents. The prepared hydrogels showed superabsorbent properties, high water‐absorption abilities and swelling rates, a lighter packing density, and a multiporous microstructure. Fourier transform infrared spectroscopy and scanning electron microscopy revealed that the sodium dodecyl sulfate surfactant, sodium bicarbonate chemical foaming agent, and 1,1,2‐trifluorotrichloroethane physical foaming agent were evenly distributed and grafted onto the PAA–Na matrix. Water‐absorption, swelling rate, and packing density testing confirmed that the superabsorbent had a high water‐absorption ability and swelling rate and a lighter packing density. Furthermore, we investigated the effects of different foaming agents, including chemical and physical foaming agents, on the swelling and water‐retention capabilities of the superabsorbent hydrogels (SAHs).The results show that the combination of these foaming agents significantly improved the water‐absorbing capacity. With the help of these foaming agents, we obtained PAA–Na hydrogels without any organic solvents for posttreatment or special porogens; this is an environmentally beneficial way to prepare SAHs for hygiene and biomedical products. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44149.  相似文献   

19.
Polyelectrolyte complex (PEC) hydrogels composed of various weight ratios of chitosan and hyaluronic acid were prepared. The PEC hydrogels were formed by the reaction of the oppositely charged chitosan polymers. The PEC films swelled in water rapidly, reaching equilibrium within 30 min, and exhibited relatively high swelling ratios, 243–322%, at 25°C. The swelling ratio increased with increasing temperature. The transport phenomena of all PEC samples were non‐Fickian and diffusion and relaxation controlled. The diffusion coefficients of the PEC films ranged from 2.22 × 10?6 to 10.05 × 10?6 cm2/s. The activation energy of the polyelectrolyte complexes ranged from 37.14 to 54.58 kJ/mol and proved to be hydrophilic. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1097–1101, 2004  相似文献   

20.
Hydrogels constitute a group of cross-linked polymeric materials with the capability of swelling and retaining large amounts of water without dissolving. In this work, the hydrogels were obtained by grafting the acrylic acid on cellulose from rice hulls and cross-linking it with glycerol, ethylene glycol, and polyethylene glycol (Mw?=?200 and 10,000 g mol?1). The samples were characterized using IR and Raman spectroscopy, the absence of the bands at 1636 and 1614 cm?1 (in IR) and at 1659 and 1637 cm?1 (in Raman), in the spectra of grafted cellulose and assigned to ν(C=C), indicated the polymerization process and the absence of the monomer residual. The cross-linking process was verified by the appearance of bands at 1090 cm?1 (IR) and 996 cm?1 (Raman), attributed to ν(C–O–C). Thermogravimetric analysis showed that the cross-linked sample with glycerol presented the lowest thermal stability. The molecular mass of CDClCC-g-AA was 55.56?±?5.21 kDa with an R2 of 0.9741 and the CDClCC average particle size of 694 nm. The topography and the average roughness of the samples were obtained by atomic force microscopy and the samples that were cross-linked with the polyethylene glycol presented greater roughness. The degree of swelling was lower in the sample cross-linked with ethylene glycol, which was related to its higher degree of cross-linking. Finally, the biocompatibility of the samples was studied by analyzing the toxic effect of the samples on human embryonic kidney cells, where results showed that samples cross-linked with ethylene glycol were non-toxic.  相似文献   

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