Thermosensitive Shape-Memory Poly(stearyl acrylate-co-methoxy poly(ethylene glycol) acrylate) Hydrogels.

Stimuli-sensitive hydrogels are highly desirable candidates for application in intelligent biomaterials. Thus, a novel thermosensitive hydrogel with shape-memory function was developed. Hydrophobic stearyl acrylate (SA), hydrophilic methoxy poly(ethylene glycol) acrylate (MPGA), and a crosslinking monomer were copolymerized to prepare poly(SA-co-MPGA) gels with various mole fractions of SA (xSA) in ethanol. Subsequently, the prepared gels were washed, dried, and re-swelled in water at 50 °C. Differential scanning calorimetric (DSC) and compression tests at different temperatures revealed that poly(SA-co-MPGA) hydrogels with xSA > 0.5 induce a crystalline-to-amorphous transition, which is a hard-to-soft transition at ~40 °C that is based on the formation/non-formation of a crystalline structure containing stearyl side chains. The hydrogels stored in water maintained an almost constant volume, independent of the temperature. The poly(SA-co-MPGA) hydrogel was soft, flexible, and deformed at 50 °C. However, the hydrogel stiffened when cooled to room temperature, and the deformation was reversible. The shape-memory function of poly(SA-co-MPGA) hydrogels is proposed for potential use in biomaterials; this is partially attributed to the use of MPGA, which consists of relatively biocompatible poly(ethylene glycol).

Hydrogel Adsorbents for the Removal of Hazardous Pollutants-Requirements and Available Functions as Adsorbent.

Over the last few decades, various adsorption functions of polymer hydrogels for the removal of hazardous pollutants have been developed. The performance of hydrogel adsorbents depends on the constituents of the gels and the functions produced by the polymer networks of the gels. Research on hydrogels utilizing the characteristic functions of polymer networks has increased over the last decade. The functions of polymer networks are key to the development of advanced adsorbents for the removal of various pollutants. No review has discussed hydrogel adsorbents from the perspective of the roles and functions of polymer networks in hydrogels. This paper briefly reviews the basic requirements of adsorbents and the general characteristics of hydrogels as adsorbents. Thereafter, hydrogels are reviewed on the basis of the roles and functions of the polymer networks in them for the removal of hazardous pollutants by introducing studies published over the last decade. The application of hydrogels as adsorbents for the removal of hazardous pollutants is discussed as well.

TiO2 Nanoparticle-Loaded Poly(NIPA-co-NMA) Fiber Web for the Adsorption and Photocatalytic Degradation of 4-Isopropylphenol.

A TiO2 nanoparticle-loaded polymer fiber web was developed as a functional material with the ability to adsorb and photo-catalytically degrade organic pollutants in aquatic media. A linear copolymer of N-isopropylacrylamide (primary component) and N-methylol acrylamide (poly(NIPA-co-NMA)) was prepared, and composite fibers were fabricated by electrospinning a methanol suspension containing the copolymer and commercially available TiO2 nanoparticles. The crosslinking of the polymer via the formation of methylene bridges between NMA units was accomplished by heating, and the fiber morphology was analyzed by electron microscopy. 4-Isopropylphenol generated by the degradation of bisphenol A-one of the endocrine-disrupting chemicals-was used as the model organic pollutant. As poly(NIPA) is a thermosensitive polymer that undergoes hydrophilic/hydrophobic transition in water, the temperature-dependence of the adsorption and photocatalytic degradation of 4-isopropylphenol was investigated. The degradation rate was analyzed using a pseudo-first-order kinetic model to obtain the apparent reaction rate constant, kapp. The enhancement of the photocatalytic degradation rate owing to the adsorption of 4-isopropylphenol onto thermosensitive poly(NIPA)-based fibers is discussed in terms of the ratio of the kapp of the composite fiber to that of unsupported TiO2 nanoparticles. Based on the results, an eco-friendly wastewater treatment process involving periodically alternated adsorption and photocatalytic degradation is proposed.

Motion-Based Detection of Lanthanides(III) Using Self-Propelled Droplets.

The directional and controllable transportation of self-propelled chemical objects in response to chemical signals in environmental media holds considerable promise for diverse applications. We investigated the chemotaxis of oil droplets loaded with surfactants to detect spatial gradients of lanthanide(III) ions, among which Dy3+ and Tm3+ were the most effective chemoattractants for steering droplets toward the targets. Patterns within a chemotactic index of the lanthanide series exhibited a convex tetrad effect and a breakpoint at Gd3+. The Jørgensen-Kawabe equation, which is based on the refined spin-pairing energy theory, quantitatively demonstrated the tetrad effect. The self-propelled droplets served as a motion-based detection mechanism for lanthanides(III).

Immobilization of Azospira sp. strain I13 by gel entrapment for mitigation of N2O from biological wastewater treatment plants: Biokinetic characterization and modeling.

Development of a strategy to mitigate nitrous oxide (N2O) emitted from biological sources is important in the nexus of wastewater treatment and greenhouse gas emission. To this end, immobilization of N2O-reducing bacteria as a biofilm has the potential to ameliorate oxygen (O2) inhibition of the metabolic activity of the bacteria. We demonstrated the effectiveness of calcium alginate gel entrapment of the nosZ clade II type N2O-reducing bacterium, Azospira sp. strain I13, in reducing levels of N2O, irrespective of the presence of O2. Azospira sp. strain I13 cells in the gel exhibited N2O reduction up to a maximum dissolved oxygen concentration of 100 µM in the bulk liquid. The maximum apparent N2O uptake rate, [Formula: see text] , by gel immobilization did not appreciably decrease, retaining 72% of the N2O reduction rate of the cell suspension of Azospira sp. strain I13. Whereas gel immobilization increased the apparent half-saturation constant for N2O, [Formula: see text] , and the apparent O2 inhibition constant, [Formula: see text] , representing the degree of O2 resistance, correspondingly increased. A mechanistic model introducing diffusion and the reactions of N2O consumption was used to describe the experimental observations. Incorporating Thieles modulus into the model determined an appropriate gel size to achieve N2O reduction even under aerobic conditions.

Propagating Precipitation Waves in Disordered Media.

The study presented in this paper investigates form changes of propagating waves generated through precipitation reactions in a gel matrix that possesses an inhomogeneous microstructure. The waves demonstrate form changes from a single ring-like pattern to multiple target-like waves. Subsequently, the waves take up a spiral form and ultimately manifest themselves in the form of a turbulence pattern that intensifies with increasing fluctuations within the gel structure. An investigation into the dynamics of the precipitation waves reveals the existence of an anomalous diffusion. The effective diffusion coefficients are found to increase linearly with the quenching temperature. Further, it is revealed through the analysis of the anomalous diffusion dynamics that precipitation patterns could be adequately controlled by adjusting the permeability fluctuations within the gel structure. The findings of this study lead to a greater understanding of the spontaneous creation of precipitation patterns by a system driven by disorder.

Propagation Properties of the Precipitation Band in an AlCl3/NaOH System.

When inherently immobile solid particles collectively form precipitates in a reaction-diffusion system involving a redissolution reaction, a propagation phenomenon may occur in which a dynamic pattern of precipitation bands forms. This propagating precipitation phenomenon has been studied by many researchers. However, two completely different processes-i.e., the reaction-diffusion of reactants and the crystal growth of products-progress simultaneously in the system, thereby rendering the phenomenon complex. There are no well-established experimental laws for this propagating precipitation phenomenon, such as the spacing, time, and width laws associated with the well-known Liesegang phenomenon, which is static in the sense that precipitation bands form and remain at the same position. In fact, it has not been clarified which of the processes controls the propagation phenomenon. Accordingly, we have investigated the apparent diffusion coefficient associated with the dynamics of propagating precipitation band in an AlCl3/NaOH system for the case in which a large excess of outer electrolytes (i.e., OH(-)) diffuses into gel in which inner electrolytes (i.e.,Al(3+)) are homogeneously distributed. An isolated precipitation band of Al(OH)3 was formed horizontally in a test tube and propagated vertically in proportion to the square root of time. In our experimental results, we found that the apparent diffusion coefficient, D(p), possesses an exponential dependence on the initial concentrations of the outer electrolyte, and the inner electrolyte; the measured relation was D(p) = D[Al(3+)](-0.6)[OH(-)](0.6), where D = (0.63 ± 0.04) × 10(5) cm(2)/s. From our model equations based on the prenucleation theory, which take into account a redissolution reaction, we found that the dynamics of the reaction front of the outer and the inner electrolytes was an important factor in controlling the propagation of the precipitation band. In our simulation results, we obtained a similar dependence of the apparent diffusion coefficient on the electrolyte concentrations.

Detection of AU(III) ions using a poly(N,N-dimethylacrylamide)-coated QCM sensor.

A polymer-coated quartz crystal microbalance (QCM) sensor has been developed for the detection of Au(III) ions in a HCl aqueous solution. Poly(N,N-dimethylacrylamide) (poly(DMAA)) gel was used as a sensing material. The poly(DMAA) gel adsorbs Au(III) ions in the HCl aqueous solution, whereas it is inactive toward most other metal ions. The equilibrium adsorption of Au(III) ions onto the poly(DMAA) gel can be expressed by the Henry-type isotherm. The oscillation behavior of the poly(DMAA)-coated QCM sensor was investigated, and linear relationships between the resonance frequency shift and the concentration of Au(III) ions were obtained for concentrations of less than 0.032 mol/m(3) (6.3 mg/m(3)) in the single and multicomponent metal systems. The poly(DMAA)-coated QCM sensor detects Au(III) ions successfully with high selectivity and sensitivity even in the presence of other metal ions and organic compounds.

Quantitative approach to ultrasonic emulsion separation.

Ultrasound of 2 MHz was irradiated to the emulsion prepared from canola oil and water and flocculation of the oil droplets occurred immediately. By putting the emulsion sample in a thin glass cell and setting it in bath type irradiation equipment, the progress of the separation was quantitatively monitored with the optical absorbance. The use of the cell enables visual observation of the behavior of oil droplets. Pictures show the formation of flocks of the dispersed phase and the appearance of checkered pattern consisting of flocks at a regular interval. The observation indicates that the action of radiation forces on oil droplets, which causes the flocculation. The flocks started to rise after stopping irradiation with holding their shape. The rising rate of the flocks was significantly greater than that of oil droplets in the original emulsion. Ultrasonic irradiation caused a rapid decrease in the absorbance, which expresses a progress of the separation. Effects of two major operation parameters, power and time on the separation degree were examined. The degree improved with increasing power input and irradiation time. The dataset was arranged in a plot of normalized separation degree against the input energy. The plot suggests that effective separation was attained with a lower power input and a longer irradiation time. The plot provides a guide for setting condition for the separation.

Preparation of poly(N-isopropylacrylamide) emulsion gels and their drug release behaviors.

Stimuli-sensitive drug delivery systems (DDSs) have attracted considerable attention in medical and pharmaceutical fields; thermosensitive DDS dealing with poly(N-isopropylacrylamide) (poly(NIPA)) have been widely studied. Novel NIPA emulsion gels, i.e., NIPA hydrogels containing distributed oil (oleyl alcohol) microdroplets, were synthesized by means of an emulsion-gelation method in which the polymerization of hydrogels in an aqueous phase in an oil-in-water (O/W) emulsion and the loading of a lipophilic drug (indomethacin) dissolved in an oil phase were accomplished simultaneously. The pulsatile (on-off) drug release from the NIPA emulsion gel loading indomethacin to a phosphate buffered saline (PBS) solution was successfully controlled by a temperature swing between 25 degrees C (release off) and 40 degrees C (release on). The mechanism of the pulsatile drug release was discussed in relation to the diffusion rate, distribution ratio, solvent exchange of NIPA hydrogels, and drug release from an NIPA organogel. The mechanism was as follows: the solvent exchange occurred within the NIPA emulsion gel (the NIPA gel-network absorbed oleyl alcohol with indomethacin) at temperatures above the LCST, and the diffusion rate of indomethacin through the solvent-exchanged gel was higher at 40 degrees C than at 25 degrees C.

Temperature-swing solid-phase extraction of heavy metals on a poly(N-isopropylacrylamide) hydrogel.

The feasibility of temperature-swing adsorption of heavy metals on a thermosensitive N-isopropylacrylamide (NIPA) hydrogel was examined. We have proposed a novel temperature-swing solid-phase extraction (TS-SPE) technique. First, a metal ion in an aqueous solution is complexed with an extractant. Subsequently, the metal-extractant complexes (or micelles) are adsorbed onto the NIPA hydrogel through a hydrophobic interaction above the lower critical solution temperature (LCST). Finally, the metal-extractant complexes are desorbed from the NIPA hydrogel after it is cooled below the LCST. In a model system consisting of Cu(II) ions, sodium n-dodecylbenzenesulfonate (SDBS), and NIPA hydrogel, the proposed TS-SPE technique has been successfully conducted. The following observations can be made: the amount of adsorbed Cu(II) ions increases with the increase in temperature, the maximum adsorption is attained at a temperature above the LCST, and the hydrogel adsorbs and desorbs Cu(II) ions reversibly due to the temperature-swing between 10 and 40 degrees C. The LCSTs of poly(NIPA) in aqueous SDBS solutions with/without CuCl2 and the surface tensions of their solutions suggest that the hydrophobicity of the complex Cu(DBS)2 is greater than the hydrophobicities of SDBS and DBS. In addition to the separation of heavy metals, TS-SPE is potentially applicable to cases such as the separation of biological molecules by means of metal-ion affinity.

Novel synthesis of macroporous poly(N-isopropylacrylamide) hydrogels using oil-in-water emulsions.

Porous N-isopropylacrylamide (NIPA) hydrogels having a unique structure, that is, spherelike cavities distributed randomly and a homogeneous network in the gel phase, were successfully synthesized by means of an emulsion templating method; this method involves the synthesis of NIPA gels in an oil-in-water (O/W) emulsion by free radical copolymerization with a cross-linker, followed by washing (removal) of the dispersed oil as a pore template (porogen). The synthesis conditions, O/W volume ratio, amount of added surfactant, and monomer concentration affect the internal pore structure, equilibrium swelling, and swelling/shrinking kinetics. A porous hydrogel swollen at 10 degrees C has a pore diameter distribution in the range of 1-40 microm, which was observed with a scanning electron microscope. Scanning electron micrographs and swelling degree reveal that the pore size and porosity can be adjusted by varying the O/W volume ratios and surfactant amounts. The porous hydrogels show very rapid swelling/shrinking in accordance with the temperature swing. The fast response is attributed to the convection flow of water through the macropores. In addition to a faster response gel, the emulsion templating method can yield potentially intelligent gels in which the pores function as spaces for reaction, separation, and storage.