Wen-Fu Lee

Superabsorbent polymeric materials. I. Swelling behaviors of crosslinked poly(sodium acrylate‐co‐hydroxyethyl methacrylate) in aqueous salt solution

A series of crosslinked poly(sodium acrylate-co-hydroxyethyl methacrylate) based on sodium acrylate (SA), 2-hydroxyethyl methacrylate (HEMA), and N,N′-methylene-bis-acrylamide (NMBA) are prepared by inverse suspension polymerization. The resultant crosslinking polymers are xerogellants. This work investigates not only the absorbency or swelling behavior for these xerogellants composed of different ratios of HEMA/SA in water, but also the effects of various salts and pH values on the swelling properties. Experimental results indicate that the absorbency in deionized water decreases with an increase in the HEMA in copolymeric gel, which is related to the degree of expansion of the network and the strength of the hydrophilic group. The absorbency in the chloride salt solutions decreases with an increase in the salt concentration (swelling is 50 times for the IA group chloride salt solutions, but is less than 5 times for the IIA group salt solution), owing to the osmosis of water and ions between the polymeric gel and the external solution. A decrease in the extent of swelling occurs for divalent and trivalent chloride salt solutions. For the salt solutions of the same ionic strength, the swelling amount has the following tendency: LiCl(aq) = NaCl(aq) = KCl(aq), CaCl2(aq) Ca2+ > Zn2+ > Cu2+. These orders are related to the complexing ability between metallic cations and the carboxylate group in the polymeric chains. Finally, the adsorption of ferric ion by these gels is also investigated.

Synthesis and solubility of the poly(sulfobetaine)s and the corresponding cationic polymers: 1. Synthesis and characterization of sulfobetaines and the corresponding cationic monomers by nuclear magnetic resonance spectra

Abstract Sulfobetaines of two types and the corresponding cationic monomers were synthesized; the preparation of their polymers is described. The solubilities and moisture regain properties of the poly(sulfobetaine)s and cationic polymers were investigated in relation to their molecular structures. It was very difficult to distinguish in 1H nuclear magnetic resonance (n.m.r.) and 13C n.m.r. spectra the chemical shift of the methylene moiety (CH2) in the neighbourhood of the quaternary ammonium group. By comparison of the chemical shifts of the corresponding cationic monomers and sulfobetaines in both 1H and 13C n.m.r. spectra, the respective methylene groups were clearly distinguished from their chemical shifts in the 1H and 13C n.m.r. spectra; the conformations of sulfobetaines and the form of cationic monomers in aqueous solution were identified.

Superabsorbent polymeric materials. II. Swelling behavior of crosslinked poly[sodium acrylate‐co‐3‐dimethyl(methacryloyloxyethyl) ammonium propane sulfonate] in aqueous salt solution

A series of xerogels based on sodium acrylate (SA), 3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate (DMAPS), and N,N′-methylene-bis-acrylamide (NMBA) are prepared by inverse suspension polymerization. The water absorbencies or swelling behaviors for these xerogels in water or various saline solutions respectively exhibit a value of 1435 g H2O/g sample and 96 g H2O/g sample of deionized water and 0.9 wt % NaCl solution at a gel containing 1.88 × 10−3 molar ratio of DMAPS while the extent of 1.53 × 10−3 molar ratio (0.25 wt % based on total monomer) of NMBA was used in the polymerization. The absorbency in the chloride salt solutions decreases with an increase in the ionic strength of salt. For the same ionic strength of various salt solutions, the swelling amount has the following tendency: Na+ > Fe3+ > A13+ > Ca2+ for the higher ionic strength of 5 × 10−3 −2 × 10−2M and Na+ > Fe3+ > Ca2+ > A13+ for the lower ionic strength of < 2 × 10−4M. The bound water found by DSC investigation is approximately equal to 2 g H2O/g sample. The pH effect and thermal effect on the water absorbency for these xerogels are also investigated.

Superabsorbent polymeric materials VIII: Swelling behavior of crosslinked poly[sodium acrylate‐co‐trimethyl methacryloyloxyethyl ammonium iodide] in aqueous salt solutions

A series of xerogels based on sodium acrylate (SA), cationic comonomer, trimethyl methacryloyloxyethyl ammonium iodide (TMMAI), and N,N-methylene-bis-acrylamide (NMBA) were prepared by inverse suspension polymerization. The water absorbency and the swelling behavior for these high absorbent polymers in deionized water and various saline solutions were investigated. Results indicated that the water absorbency for the present copolymer gel increased when a small amount of TMMAI monomer was introduced into the SA gel, then decreased with increase in TMMAI content. The water absorbency was 583 g H2O/g for a gel sample in deionized water containing 2.5 × 10−3 molar fraction TMMAI. But a contrary result was observed for initial absorption rate, that is, the initial absorption rates increased with an increase of TMMAI in deionized water and 0.9 wt % NaCl solution. The absorbency in the chloride salt solution decreased with an increase in the ionic strength of the salt solution. Finally, the adsorption of copper ion by these gels was also investigated.

Thermoreversible hydrogels X : Synthesis and swelling behavior of the (N-isopropylacrylamide-co-sodium 2-acrylamido-2-methylpropyl sulfonate) copolymeric hydrogels

A series of thermosensitive hydrogels were prepared from various molar ratios of N-isopropylacrylamide (NIPAAm) and sodium-2-acrylamido-2-methylpropyl sulfonate (NaAMPS). Factors such as temperature and initial total monomer concentration and different pH solutions were investigated. Results indicated that the more the NaAMPS content in hydrogel system, the higher the swelling ratio and the gel transition temperature; the higher the initial monomer concentration, the lower the swelling ratio. The result also indicated that the NIPAAm/NaAMPS copolymeric hydrogels had different swelling ratios in various pH environments. The present gels showed a pH-reversible property between pH 3 and pH 10 and thermoreversibility. The swelling ratios of copolymeric gels were lower in a strong alkaline environment because the gels were screened by counterions. Finally, the drug release behavior of these gels was also investigated in this article.

Superabsorbent polymeric material. V. Synthesis and swelling behavior of sodium acrylate and sodium 2-acrylamido-2-methylpropanesulfonate copolymeric gels

A series of xerogels based on sodium acrylate (SA), sodium 2-acrylamido-2-methyl propanesulfonate (NaAMPS), and N,N-methylene-bis-acrylamide (NMBA) are prepared by inverse suspension polymerization. The water absorbency and swelling behavior for these high absorbent polymers in deionized water and transition salt solutions are investigated. Experimental results indicated that the absorbency in deionized water increases with an increase of the NaAMPS content in the copolymeric gels, which is related to the degree of charge density of the network and the strength of hydrophilic group. The extent of crosslinking agent also influenced the swelling capacity because of elastic chain force of the polymer chain. The absorbency in chloride salt solutions decreases with an increase in the ionic strength of salt. But the decrease of absorbency is different in monovalent and multivalent salt solution. This behavior can be accounted for in terms of counterion condensation or screening effect for monovalent cations, as well as complexation for multivalent cations. The swelling rates in various salt solutions for these xerogels are also investigated. At last, SA-NaAMPS copolymeric gels were used for ion adsorption. But the result showed that the adsorptive amount of transition metal ions for SA-NaAMPS copolymeric gels was lower than that for pure poly(SA) gel.

Effects of surface modification of PLGA-PEG-PLGA nanoparticles on loperamide delivery efficiency across the blood–brain barrier

In this study, we developed a nanoparticle system for drug delivery across the blood–brain barrier (BBB). The nanoparticle consisting of loperamide and poly(lactide-co-glycolide)-poly(ethylene glycol)-poly(lactide-co-glycolide) (PLGA-PEG-PLGA) triblock copolymer were prepared by the nanoprecipitation method; then the nanoparticles were coated with poloxamer 188 or polysorbate 80. The effects of poloxamer 188 or polysorbate 80 on the physicochemical and pharmaceutical properties of the coated nanoparticles were investigated. Loperamide, which does not cross the blood–brain barrier (BBB) but exerts antinociceptive effects after direct injection into the brain, was encapsulated by different polymeric materials and used as a model drug. The in vitro BBB penetration study shows that the surfactant-coated PLGA-PEG-PLGA nanoparticles could have penetration of 14.4–21.2%, which was better than the PLGA-PEG-PLGA nanoparticles (PEP) (8.2%) and the PLGA nanoparticles (PN) (4.3%). The biopsy studies also confirm that the PEP coated by surfactant could increase the penetration. The results of nanoparticles accumulation in brain tissue show that the PEP coated by surfactant had a much higher concentration than both the PEP and the PN. Moreover, the maximal possible antinociception effect (MPE) for the surfactant-coated PEP was 21–35% at 150 min after administering the drug intravenously, which was significantly better than just the PEP (MPE: 11.6%). The results of the formalin test show that the surfactant-coated PEP administered intravenously 150 min prior to the formalin injection could greatly reduce the pain response in the first phase. The results demonstrate that the surfactant-coated PEP could help to deliver loperamide across the BBB.

Superabsorbent polymeric materials III. Effect of initial total monomer concentration on the swelling behavior of crosslinked poly(sodium acrylate) in aqueous salt solution

A series of xerogels based on sodium acrylate (SA) and N,N′-methylene-bisacrylamide (NMBA) were prepared by inverse suspension polymerization. The water absorbency or swelling behaviors for these hydrogels in water or various saline solutions was investigated. Experimental results indicate that the absorbency of poly(SA) in deionized water increases with decrease in the initial total monomer concentration. Results obtained from this study show that the water absorbency, respectively, exhibited a value of 992 g H2O/g sample and 106 g H2O/g sample in deionized water and a 0.9 wt % NaCl solution at an initial total monomer concentration of 3.03M. The absorbency in the chloride salt solutions decreases with increase in the ionic strength of the salt. For the same ionic strength of various salt solutions, the swelling amount has the following tendency: Co2+ > Ni2+ > Cu2+ for the higher ionic strength of 6.25 × 10−4 to 2.0 × 10−3M, and Co2+, Ni2+, and Cu2+ approximately have the same swelling amount for the lower ionic strength of < 6.25 × 10−4M. The influence of monovalent, divalent, and trivalent anions with a common cationic ion (Na+) on the water absorbency shows the tendency of monovalent < divalent < trivalent anions for the same ionic strength.

pH–thermoreversible hydrogels. II. Synthesis and swelling behaviors of N‐isopropylacrylamide‐co‐acrylic acid‐co‐sodium acrylate hydrogels

A series of pH–thermoreversible hydrogels are prepared from the three molar ratios of N-isopropylacrylamide (NIPAAm) and acrylic acid neutralized 50 mol % by sodium hydroxide (SA50) and N,N′-methylene bisacrylamide (NMBA). The influence of the environmental conditions, such as temperature and pH values, on the swelling behavior of these copolymeric gels is also investigated in this article. Results show that the hydrogels bearing negative charges exhibit different equilibrium swelling ratios under various pH media. The pH sensitivities of these gels also strongly depend on the molar ratio of SA50 in the copolymeric gels; thus, the more the SA50 content, the higher the gel pH sensitivity. These hydrogels exhibited thermosensitivity demonstrating a larger change of the equilibrium swelling ratio in aqueous media under temperature changes. An overshooting phenomenon is observed from the gel swelling kinetics under high-temperature conditions. The said hydrogels are also used to investigate the release of model drugs in this study.

Poly(2‐hydroxyethyl methacrylate‐co‐sulfobetaine) hydrogels. II. Synthesis and swelling behaviors of the [2‐hydroxyethyl methacrylate‐co‐3‐dimethyl(methacryloyloxyethyl)ammonium propane sulfonate] hydrogels

A series of the 2-hydroxyethyl methacrylate/3-dimethyl-(methacryloyloxy-ethyl)ammonium propane sulfonate (HEMA/DMAPS) copolymeric gels was prepared from various molar ratios of HEMA and the zwitterionic monomer DMAPS. The influence of the amount of the zwitterionic monomer in the copolymeric gels on the swelling behaviors in water, various saline solutions, and temperature was investigated. The results indicate that the PHEMA hydrogel (DO) and lower DMAPS content of the HEMA/DMAPS copolymeric gel (D1) exhibit overshooting phenomena in the dynamic swelling behavior. The maximum overshooting value decreases with increase in temperature. In the equilibrium swelling ratio, the PHEMA hydrogel exhibits a minimum swelling ratio at 55°C, Then, the minimum swelling ratio diminishes gradually with increasing of the DMAPS content in the HEMA/DMAPS copolymeric gels. In the saline solution, the swelling ratios of HEMA/DMAPS copolymeric gels increase rapidly with increasing of concentration of the salt with a smaller ratio of the charge/radius.