Synthesis,characterization, and rheological studies of methacrylic acid–ethyl acrylate–diallyl phthalate copolymers

Copolymerization of methacrylic acid (MAA) and ethyl acrylate (EA) was performed by the emulsion polymerization technique in the presence of a mixture of ionic and nonionic emulsifiers, at 85°C, using potassium persulfate as initiator (0.16 wt % of monomer). The molar ratio of MAA : EA varied between 44 : 56 and 54 : 46 in the monomer feed. Copolymers of MAA and EA were synthesized by incorporating diallyl phthalate (DAP) with varying concentrations (0–1.7 mol % of total monomer) in the feed. A copolymer latex of MAA, EA, and DAP was also prepared by the variable feed process. The intrinsic viscosity and gel content were determined. Copolymers were characterized by IR and NMR spectroscopic techniques. The composition of copolymers was determined by ¹H‐NMR spectra and sequential distribution from ¹³C{¹H}‐NMR spectra. The pH of the copolymer emulsion varied between 3 and 10 by addition of aqueous ammonia (23% w/w) and its effect on Brookfield viscosity was studied. The effects of copolymer composition, crosslinking agent concentration in the feed, monomer feed process, polymer solid contents, and shear rate on Brookfield viscosity were studied at pH ～ 8. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1430–1441, 2003     

Synthesis of polyamine-grafted chitosan and its adsorption behavior

The development of new environment-friendly and efficient adsorbents has attracted a great interest in recent years. In this study, ethylene diamine-grafted chitosan copolymer (CS–MAA–EN) and triethylene tetramine-grafted chitosan copolymer (CS–MAA–TN) were synthesized to remove heavy metal ions from water. The influence of pH, adsorbents dosage and initial metal concentration were investigated to study the adsorbing effect of CS–MAA–EN and CS–MAA–TN for the removal of Cu²⁺ from aqueous solutions. The equilibrium adsorption capacities of CS–MAA–EN and CS–MAA–TN were 85.91 and 102.67 mg/g, respectively. The adsorption process was fitted better by the Langmuir isotherm model (R ² = 0.9993, 0.9991) than the Freundlich isotherm model (R ² = 0.8781, 0.8775). The adsorption kinetics confirmed that the adsorption mechanism could be better described by the pseudo-second-order equation. Two adsorbents showed excellent desorption efficiency (D _e) and reuse ratio (R _u). D _e and R _u of CS–MAA–EN were evaluated as 95.2 and 89.35 %, respectively, and those values of CS–MAA–TN were 92.73 and 83.25 %. The competitive adsorption results of the two adsorbents indicated that the rate sequence was Fe³⁺ > Cu²⁺ > Cr⁶⁺ > Ni²⁺ > Zn²⁺.     

自硫化型丙烯酸酯橡胶的合成

在负离子型乳化剂的存在下,实现了丙烯酸（或甲基丙烯酸）／内烯酸乙酯／烯丙基缩水甘油醚（或甲基丙烯酸缩水甘油酯）的三元乳液共聚合,制得了主链上既带有羧基又带有环氧基的自交联型丙烯酸酯橡胶。用ＩＲ、＾１Ｈ－ＮＭＲ表征了共聚物的结构,用盐酸－丙酮法测定了共聚物中环氧基保留率。考察了多种金属离子、络合剂ＥＤＴＡ用量、交联点单体配体对共聚物凝胶质量分数的影响。     

Preparation and properties of macromolecular complexes consisting of [2-(diethylamino)ethyl]dextran hydrochloride and potassium metaphosphate

In aqueous solution [2-(diethylamino)ethyl]dextran hydrochloride (EA) was reacted with potassium metaphosphate (MPK) to form a series of water-insoluble macromolecular complexes (MC) at different hydrogen-ion concentrations (EA–MPK system). EA was also reacted with MPK in the presence of CaCl₂ (EA–MPK–CaCl₂ system). The structure and properties of MC obtained were compared with each other; elemental analysis, IR spectroscopy, solubilities, thermogravimetric analysis, and scanning electron microscopy were used to characterize these complexes. The molecular structure and properties of each MC were dependent on the hydrogen-ion concentration and whether the Ca²⁺ ion coexisted. It was suggested that MC prepared at acidic pH were composed of a relatively loose network including a small quantity of MPK, whereas those prepared at neutral and alkaline pH were composed of a relatively tight network including a large quantity of MPK. This seemed to be due to changes in the degree of dissociation and the conformation of EA and MPK with the hydrogen-ion concentration. MC in the EA–MPK–CaCl₂ system were supposed to have a rather tightly bound network structure due to the Ca²⁺ ion as compared with those in the EA–MPK system. © 1993 John Wiley & Sons, Inc.     

Amphiphilic and biocompatible properties of poly (EA‐MAA)

The amphiphilic and biocompatible behaviors of Poly (acetate‐methylacrylic acid) Poly(EA‐MAA) were investigated in this study. The aggregation behavior of Poly(EA‐MAA) in aqueous media was investigated by steady‐state fluorescence spectroscopy and surface tensiometry. The critical aggregation concentration (cac) of Poly(EA‐MAA) was determined to be ～0.03 mg/mL. Ultraviolet spectrum (UV) and fluorescence spectrum results indicated that there are interactions form between Poly(EA‐MAA) and bovine serum albumin (BSA). And β‐sheet can be changed into α‐helix of BSA in Poly(EA‐MAA) solution effectively revealed by Circular dichroism (CD), which is driven by the H‐bond and hydrophobic interactions. The good cell‐compatibility of Poly(EA‐MAA) makes it great potential in the biomedical fields. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Interaction of nafion ionomers toward various solvents

Interactions of Nafion (Naf) ionomer with water, aqueous ethanol (EA), aqueous isopropyl alcohol (IPA), and aqueous ammonia were investigated by attenuated total reflectance (ATR)–infrared (IR) spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and computational modeling studies. Microstructural features by ATR–IR revealed the existence of hydrophilic interaction of Naf with all solvents. The Naf membranes formed hydrogen bonds with water, aqueous EA, and IPA. The incorporation of solvents on the Naf matrix impaired the crystallinity, which was highest in the case of IPA. Of all the microsolvated structures of Naf investigated, the formation of H₃O⁺ ions was evident; in addition, H₅O₂⁺ ions appeared in the alcohol–water mixture, and NH₄⁺ ions were observed in the water–ammonia mixture along with a direct ion pair with the SO₃^? group in Naf. Theoretical studies based on computational modeling disclosed that the interchain distance increased with enhanced interactions (hydrophobic interactions in particular), and this was in good agreement with the highest swelling ratio of the Naf membrane in aqueous IPA and EA solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Pervaporation characteristics of methyl methacrylate–methacrylic acid copolymer membranes ionically crosslinked with metal ions for a benzene/cyclohexane mixture

Methyl methacrylate–methacrylic acid copolymer (MMA–MAA) membranes ionically crosslinked with Fe³⁺ and Co²⁺ ions (MMA–MAA–Fe³⁺ and –Co²⁺) were prepared, and characteristics of permeation and separation for a benzene/cyclohexane mixture of 50 wt % benzene through these membranes in pervaporation (PV) were studied. Although the introduction of the metal ions to the MMA–MAA membrane enhanced both benzene permselectivity and permeability for a benzene/cyclohexane mixture, the PV characteristics between the MMA–MAA–Fe³⁺ and –Co²⁺ membranes were significantly different. The difference in the PV characteristics between these membranes was strongly governed by the difference of these membrane structures based on the glass transition temperature, contact angle to methylene iodide, degree of swelling, and mixture composition absorbed in the membrane, and so on. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 233–241, 1999     

Calculation of reactivity ratios of methacrylic acid-ethyl acrylate copolymer by on-line quantitative 1H NMR spectroscopy

The solution copolymerization of methacrylic acid (MAA) and ethyl acrylate (EA) was studied by online proton nuclear magnetic resonance spectroscopy (¹H NMR) using 2,2′–azobisisobutyronitrile as an initiator in deuterated dimethyl sulfoxide at 60 °C. The chemical compositions of the copolymer and the comonomer concentrations were determined from the conversion of comonomers to copolymer by quantitative in situ NMR monitoring to estimate the reactivity ratios of the comonomers at low conversion. This is a new and easy methodology to analyze radical copolymerization. In this research, it is shown that monomer reactivity ratios can be calculated by data collected only from one initial comonomer mixture composition via online monitoring progress of the copolymerization reaction. The reactivity ratios of MAA and EA are equal to 2.360 and 0.414, respectively. This approach is used to compute the monomer reactivity ratios in a nonlinear integrated form of the copolymerization equation which is described by Mayo and Lewis terminal model. The fairly good agreement between the results and the literature data reported for the emulsion system represent the accuracy of the reactivity ratios calculated by this new approach. The calculated reactivity ratios for emulsion copolymerization are r _MAA = 2.040 and r _EA = 0.470, and the previous literature data are r _MAA = 2.580 and r _EA = 0.157.     

Chemical composition and its distribution of emulsion copolymers composed of styrene and ethyl acrylate as hydrophobic and hydrophilic comonomers

Summary Chemical composition and its distribution of styrene (St)-ethyl acrylate (EA) copolymers synthesized by emulsion copolymerization under different monomer ratios and polymerization conditions were examined by ¹H-NMR and high-performance liquid chromatography (HPLC), respectively, and compared with those of bulk copolymers. It was newly found that the chemical composition of copolymer at early stage is affected by the concentration of emulsifier (SDS, sodium dodecyl sulfate) and monomer/water ratio, and is almost independent of the concentration of initiator or polymerization temperature. The EA fraction decreased with the increase of SDS concentration and converged to the value calculated using distribution factor (f_d) when SDS concentration was extrapolated to zero. These results indicate that the EA fraction in micelle decreased compared to the expected value from f_d due to the interaction of EA monomer with emulsifier. From HPLC, it was found that each copolymer showed a sharp single peak at an early stage of polymerization indicating that no homopolymer or copolymer with different composition was produced.     

Polymer–metal composite particles: Metal particles on poly(St‐co‐MAA) microspheres

Poly(styrene‐co‐methacrylic acid) P(St‐co‐MAA) microspheres with a monodisperse size distribution were prepared by emulsifier‐free emulsion copolymerization of St and MAA. The effects of MAA content on the polymerization rate and the content of MAA in the copolymer were investigated by gravimetrical and IR methods, respectively. The results of XPS measurement indicated the presence of a carboxyl functional group. By chemical metal deposition, nickel or palladium particles were formed and deposited on the surface of P(St‐co‐MAA) microspheres to form P(St‐co‐MAA)Ni or P(St‐co‐MAA)Pd composite particles. XRD measurement and TEM observation confirmed that nickel and palladium metal particles in a small size (20–40 nm) were distributed on surface of the copolymer microspheres. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1693–1698, 2000     

Synthesis and characterization of poly(HEMA‐MAA) hydrogel carrier for oral delivery of insulin

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.     

Peroxydiphosphate–metal ion–cellulose thiocarbonate redox system‐induced graft copolymerization of vinyl monomers onto cotton fabric

The grafting of methacrylic acid (MAA) and other vinyl monomers onto cotton cellulose in fabric form was investigated in an aqueous medium with a potassium peroxydiphosphate–metal ion–cellulose thiocarbonate redox initiation system. The graft copolymerization reaction was influenced by peroxydiphosphate (PP) concentration, the pH of the reaction medium, monomer concentration, the duration and temperature of polymerization, the nature of vinyl monomers, and the nature and concentration of metallic ions (activators). On the basis of a detailed investigation of these factors, the optimal conditions for the grafting of MAA onto cotton fabric with the said redox system were as follows: [Fe²⁺] = 0.1 mmol/L, [PP] = 2 mmol/L, [MAA] = 4%, pH‐2, grafting time = 2 h, grafting temperature = 70°C, and material/liquor ratio = 1 : 50. Under these optimal conditions, the graft yields of different monomers were in the following sequence: MAA ? acrylonitrile > acrylic acid > methyl acrylate > methyl methacrylate. The unmodified cellulosic fabric (the control) had no ability to be grafted with MAA with the PP–Fe²⁺ redox system. The percentage of grafting onto the thiocarbonated cellulosic fabric was more greatly enhanced in the presence of iron salts than in their absence. This held true when the lowest concentrations of these salts were used separately. A suitable mechanism for the grafting processes is suggested, in accordance with the experimental results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1879–1889, 2003     

Vapor permeation of ethyl acetate,propyl acetate,and butyl acetate with hydrophobic inorganic membrane

This study is focused on the permeation characteristics of ester compounds from aqueous solutions through hydrophobic membrane; ethyl acetate (EA), propyl acetate (PA) and butyl acetate (BA). A surface-modified tube-type alumina membrane (Al₂O₃) was used for ester compounds recovery by vapor permeation. Experiments were performed to evaluate the effects of the feed concentration (0.15–0.60 wt.%) and feed temperature (30–50 °C) on the separation of EA, PA, and BA from dilute aqueous solutions. It was found that the permeation flux increased with increasing feed ester concentration and operating temperature. The fluxes of EA, PA, and BA at 0.60 wt.% feed concentration and 40 °C were 282, 526, 661 g/m² h, which were much higher than those of polymer membranes. The separation factors for the 0.15–0.60 wt.% feed solution of EA, PA, and BA at 40 °C were in the range of 28.1–93.9, 83.6–129.4, and 190.7–209.9, respectively. The membrane tested showed high flux and high selectivity.     

Extraction rates of amino acids by an emulsion liquid membrane with tri-n-octylmethylammonium chloride

The extraction rates of amino acids from alkaline aqueous solution into an emulsion liquid membrane containing tri-n-octylmethylammonium chloride as a carrier and Paranox 100 as an emulsifier were measured using a stirred transfer cell. The effects of agitation speed (0·33–0·66 rev s⁻¹), amino acid concentrations (0·5–50 mol m⁻³) and temperature (10–45°C) on the extraction rates were examined. The results were analyzed by a double-film model. The mass transfer coefficients of amino acids (0·26–1·58×10⁻⁵ m s⁻¹) and their complexes (0·60–1·72×10⁻⁵ m s⁻¹) were found to correlate well with the hydrophobicities of the amino acids. It was found that the surfactant layer influenced the mass transfer processes of both amino acids in the aqueous film and their complexes in the organic film. The permeation of amino acids with a large hydrophobicity through the emulsion liquid membrane was promoted by both high distribution and larger mass transfer rates. © 1998 Society of Chemical Industry     

Morphology of poly(isoprene-co-styrene-co-methacrylic acid) latex prepared by two-stage seeded emulsion polymerization

Heterogeneous latexes were prepared by a two-stage seeded emulsion polymerization process at 80°C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(styrene-co-methacrylic acid) latexes containing varying amounts of methacrylic acid (MAA) were used as seeds. The second-stage polymer was poly(isoprene-co-styrene-co-methacrylic acid). By using different methods for the addition of the MAA and by varying the amount of MAA, the hydrophilicity of the polymer phases could be controlled. The morphologies and size distributions of the latex particles were examined by transmission electron microscopy. The latexes were in all cases unimodal, and had narrow particle size distributions. The particles displayed different morphologies depending on the polymerization conditions and monomer composition. The hydrophilic properties of the two phases in combination with the internal particle viscosity and crosslinking of the second phase during polymerization were found to be the major factors influencing the particle morphology. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1543–1555, 1997     

Effect of acid and pH value on the photografting initiated by aliphatic ketones in aqueous solutions

The photografting of methacrylic acid (MAA) onto high‐density polyethylene (HDPE) initiated by aliphatic ketones (acetone, butanone, and cyclohexanone) in aqueous solutions with different pH values adjusted by adding different amount of mineral acids was reported. Acids significantly enhanced the photografting yield, and the extent of grafting generally increased with decreasing pH value. The effect of pH value on the grafting reactions varied with the acid used. The grafting of MAA onto HDPE surface was confirmed with FTIR and SEM characterizations. The water absorbency of the grafted p‐MAA varied with the extent of grafting. When the extent of grafting was less than 2000–3000 μg/cm², grafted p‐MAA absorbed about 25–30% water, whereas at higher extent of grafting, it absorbed about 50% water. The mechanism of the acid enhancement of the photografting of MAA initiated by aliphatic ketones in aqueous solutions is believed to be attributed to the change of the solubility of monomer in the solution and the conformation of grafted chains, both are favorable for accelerating grafting reactions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Margarine-Like Emulsions Prepared with Coconut and Palm Oils: Analysis of Microstructure and Freeze–Thaw Stability by Differential Scanning Calorimetry

The objective was to study the microstructure and freeze–thaw stability of margarine-like emulsions formulated with vegetable fats using differential scanning calorimetry. Emulsions were prepared with 20% w/w dispersed aqueous phase and a continuous lipid phase composed by coconut oil (CO) and/or palm oil (PO) plus polyglycerol polyricinoleate (PGPR) as emulsifier. Mean temperature (T_M) and crystallization enthalpy (ΔH_c) were obtained from the exothermic peaks corresponding to freezing of aqueous phase. Successive cooling–heating–cooling cycles were applied to analyze changes in the exothermic peak. The emulsion prepared with CO (without PO) and 1% w/w PGPR in lipid phase showed higher water droplets size (T_M = −44.8 ± 0.1 °C) and lower quantity of stabilized aqueous phase (ΔH_c = 28.9 ± 1.2 J g⁻¹) prior to application of temperature cycles, while coalescence and (presumably) water transfer processes occurred during the treatment. The use of 2% w/w PGPR was sufficient to accomplish full stabilization of aqueous phase (T_M = −45.9 ± 0.1 °C; ΔH_c = 42.6 ± 0.3 J g⁻¹) before and after the freeze–thaw treatment. The total or partial (50%) substitution of CO by PO in emulsions with 1% w/w PGPR also improved the stability of the system, exhibiting slight microstructural changes. This enhanced stability would be linked to reduced water droplets size because of more rapid crystallization of lipid phase and immobilization of aqueous phase after emulsion preparation. In conclusion, it is possible to obtain margarine-like emulsions prepared with CO and/or PO using relatively low emulsifier concentration and maintaining a desired microstructure after freeze-thawing if the percentage ratio of both fats is controlled.     

Effect of reaction medium on radical copolymerization of acrylonitrile with vinyl acids

Radical polymerization of acrylonitrile (AN) with methacrylic acid (MAA) and itaconic acid (IA) was carried out in a mixture of dimethylformamide (DMF) and water at 70°C using α, α′‐azobisisobutyronitrile (AIBN) as an initiator. Monomer feed in the polymerization vessel was 98:2 (AN:MAA/IA) in the molar ratio, and the DMF:H₂O ratio was varied between 20:80 and 80:20 (w/w). Copolymers were characterized by FTIR, carbon, hydrogen, nitrogen elemental CHN analysis, ¹H‐ and ¹³C‐NMR, and viscometry. The rate of polymerization (R_p) was found to decrease with an increase in DMF concentration in the reaction medium, that is, in 20% DMF for AN–MAA system, the R_p is 1.23% min⁻¹ in 1 h of polymerization, while in 80% DMF, R_p is reduced to 0.37% min⁻¹. The nature of the vinyl acid also affects the R_p. It has been shown that the rate of polymerization is higher for an AN–MAA system as compared to an AN–IA system (R_p = 1.0% min⁻¹) and the methacrylic or itaconic acid content in the copolymer increases with an increase in the DMF concentration. The MAA content in the poly(AN–MAA) polymer produced in 20% DMF is 3.2 mol %, which increases to 6.1 mol % (calculated through FTIR spectra) when DMF is increased to 80% in the reaction medium. The intrinsic viscosity [η] of the poly(AN–IA) and poly(AN–MAA) copolymers in DMF was found to be in the range of 0.67–2.90 dLg⁻¹ depending on the reaction medium. In determining the intrinsic viscosity, a definite deviation from rectilinearity of the concentration dependence in the high‐dilution region is observed, thereby demonstrating the polyelectrolyte behavior of these polymers. Through FTIR and NMR spectral studies, PAN homopolymer and other copolymers have shown the formation of a small quantity of acrylamide units. In addition copolymer P₁₀, which contains 10.1 mol % IA, has shown anhydride formation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1640–1652, 2001     

Characterization and in vitro drug release properties of core–shell hydrogel prepared by gamma irradiation

A hydrogel system was prepared based on core–shell approach for the delivery of trifluoperazine. Acrylonitrile (AN) core and methacrylic acid (MAA) shell copolymer were performed using gamma irradiation. The resulted system has been characterized by FTIR, TGA, TEM, and SEM techniques. The in vitro release study showed that the maximum drug released was 6.11?mg?g^?1 for AN–MAA copolymer through 120?min and 22.34?mg?g^?1 for AN-core–MAAc shell through 240?min. The results demonstrated that AN-core–MAAc had better properties than AN–MAA copolymer which means the preparation technique highly affects the properties of the system.     

Studies of adsorption of alkaline trypsin by poly(methacrylic acid) brushes on chitosan membranes

Poly(methacrylic acid)‐grafted chitosan membranes (chitosan‐g‐poly(MAA)) were prepared in two sequential steps: in the first step, chitosan membranes were prepared by phase‐inversion technique and then epichlorohydrin was used as crosslinking agent to increase its chemical stability in acidic media; in the second step, the graftcopolymerization of methacrylic acid onto the chitosan membranes was initiated by ammonium persulfate (APS) under nitrogen atmosphere. The chitosan‐g‐poly(MAA) membranes were first used as an ion‐exchange support for adsorption of trypsin from aqueous solution. The influence of pH, equilibrium time, ionic strength, and initial trypsin concentration on the adsorption capacity of the chitosan‐g‐poly(MAA) membranes have been investigated in a batch system. Maximum trypsin adsorption onto chitosan‐g‐poly(MAA) membrane was found to be 92.86 mg mL^?1 at pH 7.0. The experimental equilibrium data obtained for trypsin adsorption onto chitosan‐g‐poly(MAA) membranes fitted well to the Langmuir isotherm model. The adsorption data was analyzed using the first‐ and second‐order kinetic models, and the experimental data was well described by the second‐order equation. More than 97% of the adsorbed trypsin was desorbed using glutamic acid solution (0.5M, pH 4.0). In addition, the chitosan‐g‐ poly(MAA) membrane prepared in this work showed promising potential for various biotechnological applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008