Poly N-isopropylacrylamide Research Articles

Stopped-Flow Dynamics Study on the Escape Behavior of Polyelectrolyte Macromolecules from Microgels: The Influence of the Path Length and Size.

We reported the fabrication of several monodispersed poly(2-vinyl pyridine)-poly(N-isopropylacrylamide) (P2VP-PNIPAM) microgels including the P2VP core (non-cross-linked) and PNIPAM (cross-linked) shell by mature emulsion polymerization. The fast escape behavior (diffusion process) of linear P2VP chains through a porous PNIPAM layer was investigated by a pH jump stopped-flow apparatus. The time-dependent dynamic traces (corresponding to the scattered light intensity) decreased at the initial timescale of several seconds and then reached an apparent equilibrium, confirming the efficient escape of P2VP chains from microgels. Compared with the previously reported literature, such an accelerated escape process resulted from the sharply increased internal charge repulsive force caused by the protonation of P2VP moieties under acidic conditions. The obtained characteristic relaxation times by single exponential fitting of these kinetic traces were dependent on the final pH values, equilibrium temperatures, shell thickness (path length), and cross-linking density (mesh size). We believe that this work can provide an efficient way to investigate hindered diffusion, especially the initial rapid diffusion stage. Not only that, the proposed model can also provide theoretical guidance to some practical applications, such as membrane separation and the exocytosis phenomenon of intracellular proteins or macromolecular substances.

Rhodamine-immobilized optical hydrogels with shape deformation and Hg2+-sensitive fluorescence behaviors

A highly effective method for the research and development of a novel macroscopic hydrogel sensor and bilayer hydrogel is reported. Based on Rhodamine 6G, an Hg2+ sensitive fluorescent functional monomer was synthesized, then the monomer was utilized to synthesize hydrogel sensors and bilayer hydrogels. Hydrogel sensor has prominent selectivity to Hg2+, the bilayer hydrogel has shape changing function additionally. By combining a thermoresponsive hydrogel layer, poly N-isopropylacrylamide (PNIPAM), with an Hg2+ selective hydrogel layer via macroscopic supramolecular assembly, a bilayer hydrogel is obtained that can be tailored and reswells. The bilayer hydrogel sensor can show complex shape deformation caused by the PNIPAM layer and the Hg2+-responsive characteristic of hydrogel sensor layer can be observed under visible light or UV light. This work will provide novel insights for the design and synthesis of novel smart materials with synergistic functions.

Facile Synthesis of Fluorescence/Temperature Multisensitive Hybrid Hydrogels

Hybrid hydrogels based on poly(N-isopropylacrylamide) and poly(acrylamide) containing CdTe quantum dots with UV sensitive response and including NaYF4:Yb/Er nanoparticles have been prepared through glow discharge electrolysis plasma. The fluorescence characteristic and temperature sensitivity of the prepared hydrogels have been most extensively studied. In addition, scanning electron microscopy, X-ray diffraction, differential scanning calorimetry were determined to characterize the morphology, degree of crystallinity and the phase transformations of the hydrogels. The results suggested that the phase transition temperature of the hydrogels was 32.5°C and the hydrogels had good up-conversion and down-conversion fluorescence properties. Moreover, hybrid hydrogels had a reversible temperature response performance.

Thermo-responsive functionalized PNIPAM@Ag/Ag3PO4/CN-heterostructure photocatalyst with switchable photocatalytic activity

It is extremely important for photocatalysts to exhibit intelligent responsiveness to their environment. Herein, a poly N-isopropyl acrylamide (PNIPAM)-modified Ag/Ag3PO4-20/CN hybrid material with excellent convertible photocatalytic activity is prepared. PNIPAM has good hydrophilicity below the lower critical solution temperature (LCST); this increases the capacity of the photocatalyst for adsorbing tetracycline (TC) molecules. In addition, the PNIPAM-modified Ag/Ag3PO4-20/CN can prevent the loss of Ag3PO4. The dispersity is improved by loading g-C3N4 nanosheets (CN) for enhancing the efficiency of photocatalytic activity. Furthermore, a Z-scheme heterostructure is formed between CN and Ag3PO4, accelerating the separation efficiency of the holes and electrons. Ag nanoparticles can be used as electron-shuttle mediators, and electrons receiving more energy are transferred via the localized surface plasmon resonance (LSPR) effect. Furthermore, the PNIPAM@Ag/Ag3PO4-20/CN photocatalyst exhibits an excellent degradation rate for the degradation of TC when the temperature is lower than the LCST. The photoluminescence spectra and photocurrent curves prove that the carrier-separation efficiency of PNIPAM@Ag/Ag3PO4-20/CN is higher than those of Ag/Ag3PO4/CN and CN. The main active species of ·O2− and h+ are detected to reveal the plausible mechanism of the PNIPAM@Ag/Ag3PO4-20/CN hybrid material system. This work provides a way to develop intelligent materials for switchable photocatalytic applications.

Asymmetric Reactions in Water Catalyzed by L-Proline Tethered on Thermoresponsive Ionic Copolymers

L-Proline was covalently tethered on thermoresponsive ionic block copolymers that formed micelles in aqueous solutions. The block copolymers consisted of a poly(N-isopropylacrylamide) (PNIPAAm) segment and an anionic or cationic polymer segment. These copolymers exhibited lower critical solution temperature (LCST) behavior at ca. 35-40°C, and achieved thermal stimuli-induced formation and dissociation of micelles. The copolymer generated micelles in aqueous solution at a higher temperature, where a catalytic aldol reaction proceeded with high diastereo- and enantioselectivities. The micelles dissociated at lower temperature to form a clear solution such that the products could be efficiently extracted from the aqueous reaction mixture. Extraction of the aldol product with an organic solvent from the aqueous solution of the anionic copolymer was more efficient than from the nonionic copolymer solution.

Investigation of Gel Properties of Novel Cryo-Clay-Silica Polymer Networks.

Several methods to increase the mechanical and swelling properties of Poly(N-isopropylacrylamide) gels are known. In this study different methods were combined to systematically alter the gel properties. The combination of nanocomposite and cryo gels as well as silica post modification was used to modulate the gel strength. This new cryo-clay-silica gel based on N-isopropylacrylamide was investigated in respect to degree of swelling, kinetic of thermo responsive behavior and tensile strength. Here, the properties of new cryo-clay-silica gel were compared with properties of clay-, silica-clay and cryo-clay gels.

Multifunctional Clay/PNIPAM Hydrogel Incorporating HxMoO3 Plasmonic Quantum Dot

Functional hydrogel is becoming a frequently used material in various fields, especially in biological and medical applications. In order to overcome the barriers of low uniformity of structure and lack of energy dissipation effect in common hydrogel, in this work a strategy of doping plasmonic HxMoO3 quantum dots into PNIPAM (poly (N‐isopropylacrylamide)) hydrogel to proceed its multifunctionalization is developed. This quantum dots‐induced tactic could effectuate the enhancement of photothermal conversion, mechanical property, adhesion, and self‐healing performance simultaneously. In particular, for adhesion performance, the toughness value could be elevated to over 2500 J m−2 efficiently. Further, the enhancement mechanism behind the extraordinary adhesion performance is studied, and it can be contributed to the synergistic effect of pore structure regulation and abundant hydrogen bond, which are both beneficial to the interaction between composite hydrogel and solid surface. Subsequently, based on its extraordinary adhesion and self‐healing performance, the applicability of HxMoO3/PNIPAM hydrogel as a MØ growth substrate is investigated on wound dressing, and the experimental result demonstrates its excellent MØ growth‐promoting activity.

Investigation on the Synergistic Effect of Tetra Butyl Phosphonium Bromide with Poly(N-isopropylacrylamide) Based Kinetic Hydrate Inhibitor

The problem of clathrate hydrate plugging in flow pipes has been the most important issue in the off-shore exploitation since hydrates were found in transport facilities. In recent years, low dosage hydrate inhibitors have attracted much interest among researchers in place of thermodynamic hydrate inhibitors such as methanol and mono ethylene glycol (MEG). Poly-vinyl caprolactam and poly-isopropylacrylamide (PNIPAM) are among the hydrate inhibitors that are typically used for polymers containing amide groups. Furthermore, various kinds of polymer inhibitors containing amide group including tetrabutylphosphonium bromide(TBPB), which is a quaternary salt, were synthesized and studied in a methane gas hydrate environment. In this experiment, the injection of 0.1 wt% inhibitor at 276 K and 5 MPa was followed by stirring the water to induce nucleation. From the result, when PNIPAM alone was used as a single KHI, PNIPAM exhibited worst performance among the KHIs tested in this study. But the mixing of TBPB with PNIPAM further extended the induction time and reduced the CH4 hydrate growth rate. The real-time in situ Raman system used to understand the inhibition principle was recorded during CH4 hydrate formation, as a result, PNIPAM showed that the large hydrate cage affected, while TBPB prevented the CH4 molecule from occupying the small cage. TBPB was excellent synergist in blends with PNIPAM for kinetic hydrate inhibition of structure I forming CH4 hydrate.

Dual and Multi-Emission Hybrid Micelles Realized through Coordination-Driven Self-Assembly.

Building novel functional nanomaterials with a polymer is one of the most dynamic research fields at present. Here, three amphiphilic block copolymers of 8-hydroxyquinoline derivative motifs (MQ) with excellent coordination function were synthesized by Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) polymerization. The coordination micelles were prepared through the self-assembly process, which the MQ motifs were dispersed in the hydrophobic polystyrene (PSt) blocks and hydrophilic Poly(N-isopropylacrylamide (PNIPAM)) blocks, respectively. The dual-emission micelles including the intrinsic red light emission of quantum dots (QDs) and the coordination green light emission of Zn2+-MQ complexes were built by introducing the CdSe/ZnS and CdTe/ZnS QDs in the core and shell precisely in the coordination micelles through the coordination-driven self-assembly process. Furthermore, based on the principle of three primary colors that produce white light emission, vinyl carbazole units (Polyvinyl Carbazole, PVK) with blue light emission were introduced into the hydrophilic PNIPAM blocks to construct the white light micelles that possess special multi-emission properties in which the intrinsic red light emission of QDs, the coordination green light of Zn2+-MQ complexes, and the blue light emission of PVK were synergized. The dual and multi-emission hybrid micelles have great application prospects in ratiometric fluorescent probes and biomarkers.

Colloidal Probes of PNIPAM-Grafted SiO2 in Studying the Microrheology of Thermally Sensitive Microgel Suspensions

The complex rheology and the phase behavior of thermally sensitive poly(N-isopropylacrylamide) (PNIPAM) microgels have been investigated in both the swollen and collapsed states by using microrheology. To avoid the interactions between the tracer probes and the PNIPAM microgels, such as the adsorption or the depletion effect, the probes of silica (SiO2) particles have been grafted with PNIPAM chains (SiO2-PNIPAM) and characterized with Fourier transform infrared spectroscopy (FTIR). The successful preparation of SiO2-PNIPAM has also been proved by the investigation of the particle size and morphology with dynamic light scattering (DLS) and transmission electron microscope (TEM) below and beyond the phase transition temperature of PNIPAM. The microrheology of the PNIPAM microgel suspension has been investigated by using the prepared SiO2-PNIPAM particles as microrheological probes, and the results show that the diffusive coefficient of the probes in the swollen state is one-fifth of that in the collapsed state, and the viscosity of the PNIPAM microgel suspension in the swollen state is four times higher than that in the collapsed state, indicating SiO2-PNIPAM is a good probe in the microrheological study of PNIPAM microgel suspensions.

Collapse–Decollapse of Thermosensitive Polyelectrolyte Gels in Aqueous Media

The effect of temperature on water sorption by gels based on the copolymers of N-isopropylacrylamide with sodium p-styrene sulfonate containing 1, 3, and 5 mol % of charged monomer units is studied in aqueous media in the presence of salt (NaCl, KCl) or urea. It is shown that the incubation of gels in salt solutions leads to compression of the gels. With increasing temperature, the collapse of gels is observed in all studied media. The difference in the gel collapse temperature in water and salt solution increases with an increase in the fraction of charged units in the polymer gel network and in the salt concentration in the solution. With a return temperature decrease and gel decollapse, the mass of all gels in salt solutions (0.5–5.0 wt %) is completely restored. The incubation of gels in aqueous solutions of urea (0.5–5.0 wt %) has practically no effect on water sorption by gels before the collapse and the collapse temperature. However, the degree of swelling of polyelectrolyte gels during decollapse caused by a temperature decrease is much lower than the initial value, in contrast to the completely reversible swelling of the poly(N-isopropylacrylamide) gel under similar conditions.

Fabrication of Functional High Density Cell Sheets for Tissue Engineering Using Spin-Coated poly(N-isopropylacrylamide)Thin Films

The current goal of cell sheet engineering technology is to provide an improved approach for more predictive and effective generation of viable tissue-like constructs. Success requires validation and characterization of cell sheet growth and detachment. In this study, we perform qualitative and quantitative assessments of cell sheets lifted from thin spin-coated poly(N-isopropylacrylamide)films.

Swelling Behavior and Drug Release of Polymer Coated Nano Iron Oxide Embedded Hydroxyapatite

Spherical calcium-alginate gel beads containing HAIO, iron oxide (IO) nanoparticles embedded on hydroxapatite (HA), were prepared along with and poly (N-isopropylacrylamide) (PNIPAAM) or chitosan. These spheres, HAIO, HAIO-PNIPAAM and HAIO-chitosan spheres, were used as carriers of 5-fluorouracil (5-FU), one of the drugs for cancer chemical therapy, and the 5-FU release behavior in PBS solution was investigated at ambient and elevated temperatures using U-V spectrometry. The amount of the released 5-FU from the HAIO spheres was somewhat higher than that from HAIO-PNIPAAM and HAIO-chitosan spheres at ambient temperature. At elevated temperature, HAIO spheres showed an increase in quantity of released 5-FU. The amount of released 5-FU from HAIO-PNIPAAM spheres was almost the same, and that from HAIO-chitosan spheres was reduced compared to those at ambient temperature. These spheres, HAIO, HAIO-PNIPAAM and HAIO-chitosan spheres, show the similar swelling properties at elevated temperature. However, the combinations of Ca-alginate - PNIPAAM or Ca-alginate - chitosan may produce the different structures, which are core-shell network for HAIO-PNIPAAM spheres and or a polyelectrolyte complex for HAIO-chitosan spheres, leading to a different release behavior of 5-FU.

Visualization of the Stimuli-responsive Surface Behavior of Functionalized Wood Material by Chemical Force Microscopy

The hierarchical and porous wood structure provides a stable scaffold to design functionalized lignocellulosic materials with extended properties by chemical modification techniques. However, proper nanoscale characterization methods for these novel materials are needed to confirm the presence of the added functionality and to locate the introduced functional groups with high spatial resolution. Chemical force microscopy is a suitable characterization method to distinguish chemical surface characteristics by scanning the samples surface with a functionalized tip. We report the application of this nanotechnology method on both, unmodified and functionalized wood samples to confirm the thermo-responsive behavior of poly(N-isopropylacrylamide) (PNIPAM) modified spruce wood. By performing force measurements on ultra-microtomed surfaces, adhesion force differences on the analysed structure are monitored and reveal the location and functionality of introduced functional groups. The modified samples are scanned below and above their lower critical solution temperature with a hydrophobic tip in aqueous media to observe adhesion changes. Additionally, confocal Raman microscopy support the chemical force microscopy measurements by revealing the success of the modification and the distribution of PNIPAM across the sample cross-sections. The results show that PNIPAM is mainly located in wood cell wall areas close to the lumen in early- and transitionwood.

Gelatin interpenetration in poly N-isopropylacrylamide network reduces the compressive modulus of the scaffold: A property employed to mimic hepatic matrix stiffness.

The progression of liver disease from normal to cirrhotic state is characterized by modulation of the stiffness of the extracellular matrix (ECM). Mimicking this modulation in vitro scaffold could provide a better insight into hepatic cell behavior. In this study, interpenetrating poly(N-isopropylacrylamide-co-gelatin) cryogels were synthesized in 48 different compositions to yield scaffolds of different properties. It was observed that a high concentration of N-isopropylacrylamide (NIPAAm) leads to the formation of small pores while gelatin interpenetration on poly-NIPAAm framework renders porous structure. Swelling properties and porosity of the gels decreased with an increase in NIPAAm concentration owing to the increased compactness of the gels. Gelatin interpenetration relaxed the gels and enhanced these properties. An increase in gelatin concentration led to a reduction in compressive moduli indicating that gelatin interpenetration in the poly-NIPAAm network softens the cryogel. With the increase in NIPAAm concentration, the effect of gelatin interpenetration in reducing the compressive moduli expanded. The cytocompatibility studies indicated that the gels are cell-adherent and compatible with HepG2. Furthermore, biochemical and real-time polymerase chain reaction studies revealed that HepG2 and Huh-7 cells cultured on scaffolds mimicking the ECM stiffness of normal liver (1.5-2.5 kPa) exhibited optimum liver-specific functionalities. Increasing the stiffness to fibrotic (4-9 kPa) and cirrhotic (10-20 kPa) ECM decreases the functionality.

Thermo- and pH-Sensitive Microgels Based on Interpenetrating Networks as Components for Creating Polymeric Materials

A technique of creating films from thermo- and pH-sensitive microgels based on poly(N-isopropylacrylamide) and poly(acrylic acid) interpenetrating networks is presented. Various methods of crosslinking microgel particles into a single material are investigated. It is shown that, with increasing temperature, all films undergo a thermally induced transition from the swollen to collapsed state. The collapse time is a few seconds, which is much shorter than the collapse time of a macrogel of comparable size and similar composition.

PAM-PNIPAM/W-doped VO2 thermochromic hydrogel film with high solar modulation capability for smart windows deployment

Passively responsive thermochromic smart window, which can modulate indoor incident solar light automatically at relatively high outdoor temperature, is a practical energy-saving device for construction and automotive industries. In this paper, a thermochromic composite hydrogel film based on W-doped vanadium dioxide (W-VO2), poly N-isopropyl acrylamide (PNIPAM) and polyacrylamide (PAM) is presented and this hydrogel film was prepared between two quartz substrates to form the sandwich structured smart window. In this thermochromic system, 2 wt% monoclinic W-VO2 were dispersed in the hydrogel film with the thickness of 0.1 mm. The introduction of PAM changes the flow-state PNIPAM microgel to hydrogel, which dramatically improved the practicality of the PNIPAM-based smart window. When the outdoor temperature is higher than 40 °C, the solar modulation capacity of this passive smart window, with a high luminous transmittance of 72% at 25 °C, can reach 46.3%. The smart window possesses high solar modulation ability and more than 20% luminous transmittance even after 40 times high temperature durability tests.

Pressure-Sensitive Adhesives with Tunable Tackiness

The adhesive properties of pressure-sensitive adhesives based on interpolymer complexes of poly(vinyl caprolactam) and poly(N-isopropylacrylamide) with oligo(ethylene glycol) are studied. Poly(N-isopropylacrylamide) and poly(vinyl caprolactam) in such hydrogen-bonded complexes retain phase-separation ability in the presence of water at elevated temperatures which makes it possible to obtain adhesives that reversibly lose stickiness when heated. Analysis of the wettability of the surface of poly(vinyl caprolactam)–oligo(ethylene glycol) and poly(N-isopropylacrylamide)–oligo(ethylene glycol) films proves that tackiness is lost due to the hydrophobization of their surface during the phase transition. The switching temperature of the adhesives depends on their content of water. However, for dry compositions adhesion considerably decreases near the lower critical solution temperature.

Periodic buckling of soft 3D printed bioinspired tubes

Buckled surfaces induced by mismatched swelling and elastic properties of materials are commonly observed in nature, such as on cacti and euphorbias. The rational design and mimicry of such buckling surfaces could lead to the development of smart, adaptive, and stimuli responsive devices. We designed a 3D printed tubular structure, composed of soft swellable poly N-isopropylacrylamide (pNIPAM) segments and stiff non-swellable polyacrylamide (pAAM) segments. Similar to the shape change of Saguaro stems after rainfall, the tubes show tunable periodic buckling modes in water at the room temperature. The buckling behavior was harnessed through the development of compressive stresses in the soft swellable segments induced by the constraint of the stiff non-swellable segments. We developed a finite element model to explore the design space of this periodic buckling behavior for the tube, and used a chemo-mechanically coupled constitutive model to describe the swellable hydrogel. Inspired by the classic bar buckling problem, we constructed a phase diagram and discovered a universal design parameter that combines the effects of geometric and material properties to guide the design of periodic buckling tubes for bioinspired functional gel structures.

Scaffold-based lung tumor culture on porous PLGA microparticle substrates

Scaffold-based cancer cell culture techniques have been gaining prominence especially in the last two decades. These techniques can potentially overcome some of the limitations of current three-dimensional cell culture methods, such as uneven cell distribution, inadequate nutrient diffusion, and uncontrollable size of cell aggregates. Porous scaffolds can provide a convenient support for cell attachment, proliferation and migration, and also allows diffusion of oxygen, nutrients and waste. In this paper, a comparative study was done on porous poly (lactic-co-glycolic acid) (PLGA) microparticles prepared using three porogens—gelatin, sodium bicarbonate (SBC) or novel poly N-isopropylacrylamide [PNIPAAm] particles, as substrates for lung cancer cell culture. These fibronectin-coated, stable particles (19–42 μm) supported A549 cell attachment at an optimal cell seeding density of 250,000 cells/ mg of particles. PLGA-SBC porous particles had comparatively larger, more interconnected pores, and favored greater cell proliferation up to 9 days than their counterparts. This indicates that pore diameters and interconnectivity have direct implications on scaffold-based cell culture compared to substrates with minimally interconnected pores (PLGA-gelatin) or pores of uniform sizes (PLGA-PMPs). Therefore, PLGA-SBC-based tumor models were chosen for preliminary drug screening studies. The greater drug resistance observed in the lung cancer cells grown on porous particles compared to conventional cell monolayers agrees with previous literature, and indicates that the PLGA-SBC porous microparticle substrates are promising for in vitro tumor or tissue development.