Molecular motions in low cross-linked poly(N-isopropylacrylamide) microgels

Non-ionic N-isopropylacrylamide (PNIPAM) microgel is employed to investigate the molecular motion of polymer chains in the swollen and collapsed states. This study is performed using incoherent elastic (IES) and quasielastic neutron scattering (IQNS). IES measurements show an increase of both, the elastic intensity and the oscillations of the polymer network vibrational amplitude at the transition temperature. IQNS was measured at two different selected temperatures 290 K and 327 K corresponding to the swollen and collapsed states, respectively. The diffusion constant from IQNS experiments decreases nearly two orders of magnitude when the microgel de-swells and finally collapses.     

Relationship between the volume phase transition and the surface area of poly (N-isopropylacrylamide) and poly (N-isopropylacrylamide-co-sodium methacrylate) hydrogels

The volume phase transition of poly(N-isopropylacrylamide) (PNIPAAm) and poly(N-isopropylacrylamide-co-sodium methacrylate) (P(NIPAAm-co-SMA)) hydrogels was investigated with consideration of the pore characteristics. The volume phase transition temperature of the hydrogel increased by incorporating sodium methacrylate (SMA). Based on the BET equation, the surface area was evaluated by a gas adsorption method. The surface area of PNIPAAm and P(NIPAAm-co-SMA) hydrogels decreased with increasing temperature, resulting from the fact that the depth and the size of pores decreased significantly in the course of the volume phase transition. Hence, it is suggested that the change of surface area has a close relationship with the volume phase transition of PNIPAAm and P(NIPAAm-co-SMA) hydrogels.     

Bistable photoswitching in poly(N-isopropylacrylamide) with spironaphthoxazine hydrogel for optical data storage

A bistable switching photochromic poly(N-isopropylacrylamide) with spironaphthoxazine hydrogel copolymer (PNIPA-SPO-BIS) has been designed and synthesized by radical polymerization. The PNIPA-SPO-BIS copolymer is identified by ¹H NMR spectroscopy, FIT-IR spectroscopy and gel permeation chromatography (GPC). The morphology of the internal microstructures of the PNIPA-SPO-BIS hydrogels was observed by scanning electron microscopy (SEM). The PNIPA-SPO-BIS copolymer showed excellent photochromic behavior in water solution and in gel state. In addition, erasable and rewritable (EARW) photoimaging on the PNIPA-SPO-BIS hydrogel was successfully demonstrated. A novel optical data storage materials based on photochromic hydrogel was developed. These developments are crucial for fundamental studies and eventual technical application for all-photo mode high-density optical data storage.     

The role of water in structural changes of poly(N-isopropylacrylamide) and poly(N-isopropylmethacrylamide) studied by FTIR, Raman spectroscopy and quantum chemical calculations

Temperature-induced phase transition in water solutions of poly(N-isopropylacrylamide) (PNIPAM) and poly(N-isopropylmethacrylamide) (PNIPMAM) have been studied by ATR FTIR and Raman spectroscopy in combination with quantum chemical calculations. The presence or absence of the α-methyl group has a strong effect on the physical structure of water solutions. Although the hydrophobic interactions for PNIPMAM and PNIPAM are very similar, PNIPMAM with additional methyl group exhibits significantly weaker intermolecular interactions between the amide groups. That effect is the cause of the higher transition temperature T_t by about 8 °C for PNIPMAM compared to PNIPAM due to the formation of larger compact structures. The presence of the methyl group is significant for the reversibility of the temperature transition during the backward cooling as the dissolution of more stable compact PNIPMAM requires overcoming of a higher energy barrier and shows a strong hysteresis.     

Effect of copolymerization and semi-interpenetration with conducting polyanilines on the physicochemical properties of poly(N-isopropylacrylamide) based thermosensitive hydrogels

Thermosensitive hydrogels are made by radical homopolymerization of N-isopropylacrylamide (NIPAAM) or copolymerization of NIPAAM with 2-acrylamido-2-methyl-propane sulfonic acid (AMPS). The networks are semi-interpenetrated (s-IPN) with linear conducting polymers: polyaniline (PANI) or poly(N-methylaniline) (PNMANI). The semi-interpenetration affect slightly the phase transition temperature (measured by DSC) of the hydrogels, while water uptake capacity is strongly affected and depends on the relative hydrophobicity of the conducting polymer. Since polyanilines can be protonated in aqueous media, the swelling capacity of the s-IPN hydrogel depends strongly on pH unlike the unmodified hydrogel. The release of a model compound (tris(2,2′-bipyridine)ruthenium (II), ), driven by swelling or temperature, is also strongly affected both by the introduction of sulfonic groups, by copolymerization of NIPAAM with AMPS, semi-interpenetration and on the hydrophobicity of the conducting polymer. In that way, composite materials with quite different ion exchange behavior can be made by copolymerization and conducting polymer interpenetration.     

Synthesis of gold nanoparticles stabilized with poly(N-isopropylacrylamide)-co-poly(4-vinyl pyridine) colloid and their application in responsive catalysis

The copolymer of poly(N-isopropylacrylamide)-co-poly(4-vinylpyridine) was synthesized by free radical copolymerization of 4-vinylpyridine and N-isopropylacrylamide. The copolymer synthesized with the feed monomer ratio of 4-vinylpyridine/N-isopropylacrylamide equal to 1/3 was associated to form thermoresponsive colloid in neutral water at room temperature, the average size and the cloud-point temperature of which were 40 nm and 32 °C, respectively. The thermoresponsive colloid was used as scaffold to load 2-nm Au nanoparticles to form the responsive catalyst of colloid-stabilizing gold nanoparticles. The catalysis in the model reduction of 4-nitrophenol with NaBH₄ suggested that the catalytic reduction could be modulated due to the thermoresponsive phase-transition of the colloid-stabilizing gold nanoparticles. That was, the catalytic reduction firstly accelerated with the increase in temperature below the cloud-point temperature and then decelerated with the increase in temperature above the cloud-point temperature of the thermoresponsive colloid-stabilizing Au nanoparticles.     

A new insight in the dynamo-mechanical behavior of poly(ethylene terephthalate)

Dynamic mechanical experiments performed on a semicrystalline sample of poly(ethylene terephthalate) evidenced the relaxation processes (α and β) that occur in the polymer. Multifrequency experiments were used both in order to calculate the apparent activation energy of relaxation and to point out how the dynamic conditions alter not only the main relaxations, but the overlapping melting/recrystallization events that succeed after the glass transition. Heating rate seems to affect these phenomena in a way similar to frequency. Also, a consecutive heating step was carried out to support the statements.     

Transport properties of ions through temperature-responsive charged membranes prepared using poly(vinyl alcohol)/poly(N-isopropylacrylamide)/poly(vinyl alcohol-co-2-acrylamido-2-methylpropane sulfonic acid)

Temperature-responsive charged membranes were prepared from the polymer mixture of poly(vinyl alcohol) (PVA), in situ polymer of N-isopropylacrylamide (NIPAAm) and PVA, and a polyanion [poly(vinyl alcohol-co-2-acrylamido-2-methylpropane sulfonic acid)]. The membranes were cross-linked under several conditions. The relationship between the preparation conditions and the water content response to temperature change, rH, and the charge density response to temperature change, rCx, was investigated. The membrane cross-linked with glutaraldehyde after annealing has the highest rH and rCx in all the membranes. rCx decreases with increasing polyanion content, and increases with increasing poly(NIPAAm) content. Permeation experiments in a dialysis system consisting of the membrane and mixed KCl and CaCl₂ solutions show that the transport modes of Ca²⁺ ions through the membrane are controlled by temperature changes in two ways: downhill transport (transport along their own concentration gradient in a system) at temperatures below the lower critical solution temperature (LCST) of poly(NIPAAm); uphill transport (transport against their concentration gradient) at temperatures above the LCST.     

The conformational effect of form I helical poly(L-proline) and form II helical poly(L-proline) to the complex formation with helical poly(L-glutamic acid) through hydrogen bonding

The complex formation between helical poly-L-glutamic acid (PLGA) and helical poly-L-proline (PLP) was studied in a methanol-water (2 : 1) cosolvent and a propanol-water cosolvent (9 : 1). Reduced viscosity, circular dichroism, pH, and molar absorptivity were measured. The experimental results exhibit that the interpolymer complex was formed between helical PLGA and helical PLP through hydrogen bonding. When the complex was formed the unit mole ratio of PLGA : PLP(II) is 2 : 1 and PLGA : PLP(I) is 1.5 : 1, the ability of complex formation of PLP (II) with PLGA is better than that of PLP(I). On complexation the conformations of PLGA and PLP change and this change is more enhanced in the PLGA-PLP(II) than the PLGA-PLP(I) complex; its cause is studied. © 1993 John Wiley & Sons, Inc.     

Assembly of nanotubes of poly(4-vinylpyridine) and poly(acrylic acid) through hydrogen bonding

Nanotubes of poly(4-vinylpyridine) (PVP) and poly(acrylic acid) (PAA) were fabricated by hydrogen bonding based on layer-by-layer (LbL) assembly. The uniform and flexible tubular structures were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). FTIR and X-ray photoelectron spectroscopy (XPS) measurements confirm the formation of hydrogen bonds in the assembled nanotubes. PAA can be released from the assembled PAA/PVP nanotubes in a basic aqueous solution to give the walls of the tubes a porous structure. Such assembled nanotubes can be considered as carriers for catalysts or drugs, especially in aqueous solution against capillary force.     

On the triplet state of poly(N-vinylcarbazole)

Triplet state properties including transient triplet absorption spectrum, intersystem crossing yields in solution at room temperature and phosphorescence spectra, quantum yields and lifetimes at low temperature as well as singlet oxygen yields were obtained for poly(N-vinylcarbazole) (PVK) in 2-methyl-tetrahydrofuran (2-MeTHF), cyclohexane or benzene. The results allow the determination of the energy value for the lowest lying triplet state and also show that triplet formation and deactivation is a minor route for relaxation of the lowest excited singlet state of PVK. In addition, they show the triplet state is at higher energy than reported heavy metal dopants used for electrophosphorescent devices, such that if this is used as a host it will not quench their luminescence.     

Radiation polymerization of thermo-sensitive poly (N-vinylcaprolactam)

Temperature-sensitive poly (N-vinylcaprolactam) both in water-soluble state and in gel was prepared by γ-radiation polymerization. The effects of radiation dose, radiation dose rate and monomer concentration on polymerization and the low critical solution temperature characteristics of the polymer were studied. The results show that the polymer prepared within certain radiation dose (beyond 2 kGy) and dose rate range (2–14 Gy/min) has good temperature sensitivity and uniformity.     

Molecular and crystal structures of N,N′-propylene- and N,N′-phenylene-diylbis [3-(1-aminoethyl)-6-methyl-2H-pyran-2,4(3H)-dione]

Two macrocyclic ligands, N,N′-propylene-diylbis[3-(1-aminoethyl)-6-methyl-2H-pyran-2,4(3H)-dione] I and N,N′-phenylene-diylbis[3-(1-aminoethyl)-6-methyl-2H-pyran-2,4(3H)-dione] II, have been prepared by the condensation of dehydroacetic acid (3-acetyl-4-hydroxy-6-methyl-2H-pyran-2-one) with 1,2-phenylenediamine and 1,3-propylenediamine. They have been characterized by means of elemental analysis, IR spectroscopy as well as by X-ray crystallography. The molecular structures of the compounds I and II can be described as consisting of two β-enaminone-2-pyrone rings interlaced with either alkyl chain in I or phenyl ring in II. The X-ray studies confirmed the existence of strong N–HO intramolecular hydrogen bonds in both structures. Their lengths are in accordance to lengths of RAHB intramolecular hydrogen bonds in 1,3-diketones, aryl-hydrazones, β-enaminones and related heterodienes (2.5–2.6 Å) [P. Gilli, V. Bertolasi, V. Ferretti and G. Gilli, J. Am. Chem. Soc., 122 (2000) 10405].     

Effective fixation of carbon dioxide into poly(glycidyl methacrylate) in the presence of pyrrolidone polymers

The homopolymer (PGMA) of glycidyl methacrylate (GMA) and the copolymer of GMA with N‐vinyl‐2‐pyrrolidone were prepared under radical conditions and employed for the fixation of CO₂ with LiBr as a catalyst, in which the oxirane groups were transformed into five‐membered cyclic carbonate groups. For the fixation of CO₂ into the oxirane groups on PGMA, poly(N‐vinyl‐2‐pyrrolidone), in which the catalyst was impregnated before the reaction, was found to be an effective additive. This was exploited for the reaction using the copolymer containing both the oxirane and pyrrolidone moieties. The oxirane groups on the copolymer were also converted readily to the cyclic carbonates through the fixation of CO₂. In such use of the pyrrolidone structures on the polymers, the fixation of CO₂ could be carried out effectively in a diluted chlorobenzene solution and also under solvent‐free conditions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4578–4585, 2005     

Fe3O4/N-异丙烯酰胺(PNIPAM)纳米颗粒的合成

A magnetic and thermosensitive poly(N-isopropylacrylamide)(PNIPAM) nanoparticles were prepared by the following procedure. The core-shell composite microparticles were synthesized by precipitating polymerization with Fe₃O₄ being entrapped with SiO₂ as core and cross-linked PNIPAM as shell. Then， the SiO₂ core was etched by hydrofluoric acid and magnetic thermosensitive Fe₃O₄/PNIPAM particles were formed. It has also been shown that the Fe₃O₄/PNIPAM nanoparticles are featured by lower critical solution temperature (LCST) at 33.0 ℃ while the temperature varies from 28.0 ℃ to 36.0 ℃. The composite magnetic thermosensitive particles were characterized by XRD， SEM， TEM and FTIR. The synthetic mechanism is also discussed.     

Tough and fluorescent hydrogels composed of poly(hydroxyurethane) and poly(stearyl acrylate-co-acrylic acid) with hydrophobic associations and hydrogen bonds as the physical crosslinks

Fluorescent hydrogels have promising applications in biomedical and engineering fields. However, they are usually mechanically weak. Here, we report a fluorescent composite hydrogel with high toughness, which is facilely prepared by solution casting ethanol solution of poly(hydroxyurethane) (PHU) and poly(stearyl acrylate-co-acrylic acid) (P[SA-co-AAc]) followed by swelling the casted film in water. The composite hydrogels with water content of 62–78 wt% possess remarkable mechanical performances, with tensile breaking stress of 0.3–1.1 MPa, breaking strain of 280%–400%, Young's modulus of 0.2–0.7 MPa, and tearing fracture energy of 1250–2630 J/m². The high toughness is attributed to the effective energy dissipation of the network with hydrophobic association of SA units and hydrogen bonds between PHU and P(SA-co-AAc) as the physical crosslinks. The intense aggregation of carbamates and the formation of carbamate clusters through intra- and intermolecular hydrogen bonds endow the composite hydrogel with strong fluorescence. These hydrogels with high toughness and strong fluorescence should find applications in flexible electronics, information display, and biomedical devices.     

Infrared characterization of poly(vinyl cinnamate) and its blends with poly(4-vinyl phenol) before and after UV exposure

The results of an infrared spectroscopic characterization of poly(vinyl cinnamate) (PVCIN) and its blends with poly(4-vinyl phenol) (PVPh) are reported before and after photo-crosslinking the PVCIN by exposure to UV radiation. The purpose of this article is to demonstrate methodology, and it is shown that quantitative analysis of the fraction of unsaturated ( CC ) double bonds, “free” (non-hydrogen bonded) and hydrogen bonded unsaturated ( CO CC ) and saturated ( CO C C ) acetoxy carbonyl groups is feasible in these blends as a function of UV exposure time. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1579–1590, 1998