一步法制备PNIPAAm-g-PAN/PSt载银复合微球及其抗菌性能研究

以AgNO3为金属源,通过乙醇将与聚N-异丙基丙烯酰胺接枝聚丙烯腈/聚苯乙烯（PNIPAAm-g-PAN/PSt）聚合物微球表面酰胺基团配位的银离子（Ag+）还原,一步法制备了PNIPAAm-g-PAN/PSt载银复合微球。通过傅立叶变换红外（FTIR）和紫外-可见光光谱表征发现,由Ag+还原所得的Ag纳米颗粒被成功地固载在PNIPAAm-g-PAN/PSt 微球上;用透射电子显微镜（TEM）对载银微球的大小和形态进行了表征;热重分析（TGA）结果表明,固载在微球表面的银纳米颗粒的含量（质量分数）为12%;抗菌实验结果表明,所制备的载银微球具有抗革兰氏阴性菌的活性。     

Assembly of Preformed Gold Nanoparticles onto Thermoresponsive Poly(N‐isopropylacrylamide)‐Based Microgels on the Basis of Au‐thiol Chemistry

The assembly of preformed gold nanoparticles (AuNPs ) onto the thermoresponsive poly(N ‐isopropylacrylamide) (PNIPAM )‐based microgels was achieved on the basis of the driving force of Au‐thiol chemistry. The loading amount of AuNPs can be controlled by varying the ratio of AuNPs relative to PNIPAM ‐based microgels. The as‐prepared PNIPAM /Au hybrid microgels showed well‐defined reversible swelling/deswelling transition in response to temperature, which can be employed to tune the plasmonic property of hybrid microgels. As the temperature was increased, the position of localized surface plasmon resonance (LSPR ) band red‐shifted to some extent mainly due to the increase in the local refractive index around AuNPs .     

Novel silver‐loaded semi‐interpenetrating polymer network gel films with antibacterial activity

Novel semi‐interpenetrating polymer networks (SIPNs) based on segmented polyurethane‐urea and poly(N‐isopropylacrylamide‐co‐acrylic acid‐co‐butylmethacrylate) (poly(NIPAM‐co‐AA‐BMA)) were synthesized for the fabrication of silver nanoparticles (AgNPs) in the SIPN system that could be useful for wound dressing applications. The obtained SIPN films, after neutralization, showed high swelling in aqueous environments and good mechanical properties in both dry and hydrated states. Analysis of the dried SIPN films by differential scanning calorimetry and dynamic viscoelastic measurements revealed the presence of crosslinked copolymers as well as homopolymers in the SIPN system. The neutralized swollen SIPN film coordinated with the silver ions (Ag⁺) that were incorporated into it. AgNPs were subsequently formed by the reduction of Ag⁺. The formation of AgNPs was characterized by UV‐visible spectroscopy, atomic force microscopy, wide‐angle X‐ray diffraction, and thermogravimetric analysis (TGA). Bactericidal activity tests revealed a distinct zone of microbial inhibition within and around the silver‐doped SIPN films. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4950–4962, 2009     

Supramolecular photocatalyst of Palladium (II) Encapsulated within Dendrimer on TiO2 nanoparticles for Photo‐induced Suzuki‐Miyaura and Sonogashira Cross‐Coupling reactions

In this study, synthesis, characterization and catalytic performance of a novel supramolecular photocatalytic system including palladium (II) encapsulated within amine‐terminated poly (triazine‐triamine) dendrimer modified TiO₂ nanoparticles (Pd (II) [PTATAD] @ TiO₂) is presented. The obtained nanodendritic catalyst was characterized by FT‐IR, ICP‐AES, XPS, EDS, TEM, TGA and UV‐DRS. The as‐prepared nanodendritic catalyst was shown to be highly active, selective, and recyclable for the Suzuki–Miyaura and Sonogashira cross‐coupling of a wide range of aryl halides including electron‐rich and electron‐poor and even aryl chlorides, affording the corresponding biaryl compounds in good to excellent yields under visible light irradiation. This study shows that visible light irradiation can drive the cross‐coupling reactions on the Pd (II) [PTATAD] @ TiO₂ under mild reaction conditions (27–30 °C) and no additional additives such as cocatalysts or phosphine ligands. So, we propose that the improved photoactivity predominantly benefits from the synergistic effects of Pd (II) amine‐terminated poly (triazine‐triamine) dendrimer on TiO₂ nanoparticles that cause efficient separation and photogenerated electron–hole pairs and photoredox capability of nanocatalyst which all of these advantages due to the tuning of band gap of catalyst in the visible light region.     

Selenium‐Modified Microgels as Bio‐Inspired Oxidation Catalysts

Active colloidal catalysts inspired by glutathione peroxidase (GPx) were synthesized by integration of catalytically active selenium (Se) moieties into aqueous microgels. A diselenide crosslinker (Se X‐linker) was successfully synthesized and incorporated into microgels through precipitation polymerization, along with the conventional crosslinker N,N′‐methylenebis(acrylamide) (BIS). Diselenide bonds within the microgels were cleaved through oxidation by H₂O₂ and converted to seleninic acid whilst maintaining the intact microgel microstructure. Through this approach catalytically active microgels with variable amounts of seleninic acid were synthesized. Remarkably, the microgels exhibited higher catalytic activity and selectivity at low reaction temperatures than the molecular Se catalyst in a model oxidation reaction of acrolein to acrylic acid and methyl acrylate.     

Preparation of polypyrrole‐graft‐poly(N‐isopropylacrylamide)/silver nanocomposites from pyrrolyl‐capped macromonomer by AgNO3 and their stimuli responsibility of light emission

Pyrrolyl‐capped poly(N‐isopropylacrylamide) macromonomers (Py‐PNIPAM) were prepared through reversible addition‐fragmentation‐transfer polymerization with benzyl 1‐pyrrolylcarbodithioate as chain‐transfer agent. Polymerizations of Py‐PNIPAM with/without pyrrole using AgNO₃ as oxidizing agent and dimethylforamide as solvent resulted in graft copolymers of polypyrrole‐graft‐poly(N‐isopropylacrylamide) (PPy‐g‐PNIPAM) as well as silver nanoparticles, leading to the formation of PPy‐g‐PNIPAM/silver nanocomposites. The resulting nanocomposites were soluble in water when the content of PPy was low, and when the molar ratio of Py/Py‐PNIPAM increased to 30, the resulting products became insoluble in water. The resulting nanocomposites had special optical properties because of PPy as well as the temperature‐responsible PNIPAM. The chemical structure and composition of nanocomposite were characterized by ¹H nuclear magnetic resonance spectroscopy, gel permeation chromatograms, fourier transform infrared spectroscopy, and X‐ray diffraction. Their optical properties were characterized by UV–vis and fluorescence spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6950–6960, 2008     

Fabrication of silver nanoparticles in pH responsive polymer microgel dispersion for catalytic reduction of nitrobenzene in aqueous medium

Copolymer microgels based on N-isopropylacrylamide (NIPAM) and methacrylic acid (MAA) have been synthesized by free radical emulsion polymerization using N,N-methylenebisacrylamide (BIS) as a cross-linker. Synthesized microgels were characterized by Fourier transform infrared spectroscopy (FTIR). Then silver nanoparticles were fabricated in the synthesized microgels by in-situ reduction of AgNO₃ with NaBH₄. The formation of silver nanoparticles was confirmed by UV–Vis spectroscopy. The pH sensitivity of the copolymer microgels was investigated using dynamic light scattering technique (DLS). Hydrodynamic radius of P (NIPAM–MAA) microgels increases with increase in pH of the medium at 25°C. Surface plasmon resonance wavelength (λ_SPR) of silver nanoparticles increases with increase in hydrodynamic radius due to change in pH of the medium. The catalytic activity for the reduction of nitrobenzene (NB), an environmental pollutant, into aniline was investigated by UV–Vis spectroscopy in excess of NaBH₄ using hybrid microgels as catalyst. The value of apparent rate constant (k_app) of the reaction was calculated using pseudo first order kinetic model and it was found to be linearly related to the amount of catalyst. The results were compared with literature data. The system was found to be an effective catalyst for conversion of NB into aniline.     

Synthesis and characterization of water‐soluble gold nanoparticles stabilized by comb‐shaped copolymers

The water‐soluble gold nanoparticles stabilized by well‐defined comb‐shaped copolymers have been synthesized successfully. The hybrid nanoparticles consist of gold core and poly[poly(ethylene oxide) methyl ether acrylate]‐block‐poly(N‐isopropylacrylamide) [P(A‐MPEO)‐block‐PNIPAM] shell. The water‐soluble comb‐shaped copolymers, P(A‐MPEO)‐block‐PNIPAM with PNIPAM as a handle, were successfully synthesized via a macromonomer technique using reversible addition fragmentation chain transfer (RAFT) polymerization method. The terminal dithioester group of the comb‐shaped copolymer was reduced to a thiol end group forming SH‐terminated copolymers, P(A‐MPEO)‐block‐PNIPAM‐SH. Successively they were used to stabilize gold nanoparticles by the “grafting‐to” approach. The hybrid nanoparticles were characterized by TEM, UV–vis, and HRTEM. Because of the thermosensitive property of PNIPAM in aqueous solution, the comblike copolymer‐tethered gold nanoparticles show a sharp and reversible phase transition at 30 °C in aqueous solution, which was determined by microdifferential scanning calorimetry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 341–352, 2008     

Sulfonated palladium(II) N‐heterocyclic carbene complex immobilized on nano–micro size poly(4‐vinylpyridinium chloride) for Suzuki‐Miyaura cross‐coupling reaction

The sulfonated palladium(II) N‐heterocyclic carbene complex Pd^II(NHC)SO₃^?, supported on poly(4‐vinylpyridinium chloride), was used as a heterogeneous, recyclable and active catalyst for the Suzuki–Miyaura reaction. This catalyst was applied for coupling of various aryl halides with phenylboronic acid and the corresponding products were obtained in excellent yields and short reaction times. The catalyst was characterized using Fourier transform infrared and diffuse reflectance UV–visible spectroscopies, scanning electron microscopy and elemental analysis. After each reaction, the catalyst was recovered easily by simple filtration and reused several times without significant loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and characterization of temperature‐ and pH‐responsive diblock copolymers and their silica‐coated nanoparticles

Multiresponsive amphiphilic poly(N,N‐dimethylaminoethyl methacrylate)‐b‐poly(N‐isopropylacrylamide) (PDMAEMA‐b‐PNIPAM) was successfully synthesized by reversible addition‐fragmentation chain transfer polymerization. Poly(N,N‐dimethylaminoethyl methacrylate)‐b‐poly(N‐isopropylacrylamide) has thermal and pH stimuli responsiveness. Their lower critical solution temperature and hydrodynamic radius can be adjusted by varying the copolymer composition, block length, solution pH, and temperature. In addition, a convenient method has been established to prepare cross‐linked silica‐coated nanoparticles with PDMAEMA‐b‐PNIPAM micelles as a template, resulting in good organic/inorganic hybrid nanoparticles defined as 175 to 220 nm. The structure and morphology were characterized by proton nuclear magnetic resonance (₁HNMR), Fourier‐transform infrared spectroscopy (FT‐IR), transmission electron microscopy (TEM), and transmission electron microscopy‐energy dispersive X‐ray spectroscopy (TEM‐EDS).     

Thermosensitive and control release behavior of poly (N‐isopropylacrylamide‐co‐acrylic acid) latex particles

In this work, poly(N‐isopropylacrylamide‐co‐acrylic acid) (poly(NIPAAm‐AA)) copolymer latex particles (microgels) were synthesized by the method of soapless emulsion polymerization. Poly(NIPAAm‐AA) copolymer microgels have the property of being thermosensitive. The concentration of acrylic acid (AA) and crosslinking agent N,N′‐methylenebisacrylamide were important factors to influence the lower critical solution temperature (LCST) of poly(NIPAAm‐AA) microgels. The effects of AA and crosslinking agent on the swelling behavior of poly(NIPAAm‐AA) microgels were also studied. The poly(NIPAAm‐AA) copolymer microgels were then used as a thermosensitive drug carrier to load caffeine. The effects of concentration of AA and crosslinking agent on the control release of caffeine were investigated. How the AA content and crosslinking agent influenced the morphology and LCST of the microgels was discussed in detail. The relationship of morphology, swelling, and control release behavior of these thermosensitive microgels was established. A new scheme was proposed to interpret the control release of the microgels with different morphological structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5734–5741, 2008     

Controlled post‐synthesis grafting of thermoresponsive poly(N‐isopropylacrylamide) on mesoporous silica nanoparticles

Ordered mesoporous silica nanoparticles with pore diameter of 5 nm were synthesized by modification of the sol‐gel synthesis method. Post‐synthesis two‐step grafting of thermoresponsive poly(N‐isopropylacrylamide) inside the mesopores of the nanoparticles was carried out by distillation–precipitation polymerization of the methacryloxy‐functionalized mesoporous nanoparticles with N‐isopropylacrylamide monomer. A precise control on the quantity of the grafted polymer was achieved by changing the ratio of monomer to methacryloxy‐functionalized nanoparticles. The polymer‐grafted hybrid nanoparticles obtained were fully characterized by infrared spectroscopy, X‐ray diffraction, dynamic light scattering, transmission electron microscopy, thermal, and gas‐volumetric analyses, which clearly showed presence and thermoresponsive behavior of the polymer inside the mesopores with the preservation of the characteristic mesoporous structure of the nanoparticles. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of multifunctional polymer containing Ni‐Pd NPs via thiol‐ene reaction for one‐pot cascade reactions

Recently, acid–base bifunctional catalysts have been considered due to their abilities, such as the simultaneous activation of electrophilic and nucleophilic species and their high importance in organic syntheses. However, the synthesis of acid–base catalysts is problematic due to the neutralization of acidic and basic groups. This work reports a facial approach to solve this problem via the synthesis of a novel bifunctional polymer using inexpensive materials and easy methods. In this way, at the first step, heterogeneous poly (styrene sulfonic acid‐n‐vinylimidazole) containing pentaerythritol tetra‐(3‐mercaptopropionate) (PETMP) and trimethylolpropane trimethacrylate (TMPTMA) cross‐linkers were synthesized in the pores of a mesoporous silica structure using click reaction as a novel bifunctional acid–base catalyst. After that, Ni‐Pd nanoparticles supported on poly (styrenesulfonic acid‐n‐vinylimidazole)/KIT‐6 as a novel trifunctional heterogeneous acid–base‐metal catalyst was prepared. The prepared catalysts were characterized by various techniques like FT‐IR, TGA, ICP‐AES, DRS‐UV, TEM, FE‐SEM, EDS‐Mapping, and XRD. The synthesized catalysts were efficiently used as bifunctional/trifunctional catalysts for one‐pot, deacetalization‐Knoevenagel condensation and one‐pot, three‐step and a sequential reaction containing deacetalization‐Knoevenagel condensation‐reduction reaction. It is important to note that the synthesized catalyst showing high chemo‐selectivity for the reduction of nitro group, alkenyl double bond and ester group in the presence of nitrile. Moreover, it was found that the different nanoparticles including Ni, Pd, and alloyed Ni‐Pd showing different chemo‐selectivity and catalytic activity in the reaction.     

New Route to Smart Core‐Shell Polymeric Microgels: Synthesis and Properties

Summary: A new method has been developed to prepare smart polymeric microgels that consist of well‐defined temperature‐sensitive cores with pH‐sensitive shells. The microgels were obtained directly from aqueous graft copolymerizations of N‐isopropylacrylamide and N,N‐methylenebisacrylamide from water‐soluble polymers containing amino groups such as poly(ethyleneimine) and chitosan. The gel diameters ranged from 300 to 400 nm. The unique core‐shell nanostructures, which had narrow size distributions, exhibited tuneable responses to pH and temperature.

Transmission electron micrograph of the poly(N‐isopropylacrylamide)/chitosan core‐shell microgels.     

Synthesis of thermo‐responsive microgels in supercritical carbon dioxide using ethylene glycol dimethacrylate as a cross‐linker

Herein, we report the preparation of thermo‐responsive polymers in a green medium. The white, dry, fine powders were obtained directly from the cross‐linking polymerization of N‐isopropylacrylamide (NIPA) in supercritical carbon dioxide (scCO₂) at pressures ranging from 10 to 28 MPa utilizing ethylene glycol dimethacrylate (EGDMA) as a cross‐linker. The effects of reaction pressure, cross‐linker ratio, initiator concentration, and reaction time were investigated. In the presence of this cross‐linker (26.4% w/w), much smaller poly(N‐isopropylacrylamide) (PNIPA) microgels (<0.2 µm diameter) were formed, and it was shown that the particle size and the morphology of the polymer were strongly dependent on the cross‐linker ratio in scCO₂. Copyright © 2009 John Wiley & Sons, Ltd.     

Photo‐triggered microgel aggregation using o‐nitrobenzaldehyde as aggregating power source

In this work, cationic and anionic microgels which are mainly formed from thermal responsive polymer, poly(N‐isopropylacrylamide), are prepared and mixed in water. These microgels interact with each other due to the electrostatic interaction, and aggregate voluntarily. By applying the microgel aggregating system, photo‐responsive aggregating system is constructed by using o‐nitrobenzaldehyde (NBA), which reacts and releases hydrogen triggered by photo stimuli. The microgel aggregates in an aqueous solution of NBA re‐disperse depending on the irradiation time of UV light. In addition, by masking the UV irradiated area, the resultant shapes of microgel aggregates are controlled. The aggregated microgel shows rapid and drastic volume changes in response to heat. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1317‐1322     

Polypyrrole/poly(N‐isopropylacrylamide‐co‐acrylic acid) thermosensitive and electrically conductive composite microgels

The electrically conductive polypyrrole/dodecylbenzene sulfonic acid/poly(N‐isopropylacrylamide‐co‐acrylic acid) (PPy/DBSA/poly(NIPAAm‐co‐AA)) composite microgels were synthesized by a chemical oxidation of pyrrole in the presence of DBSA as the primary dopant, and poly(NIPAAm‐co‐AA) microgels as the polymeric codopant and template, in which APS was used as the oxidant. It was proposed to prepare “intelligent” polymer microgel particles containing both thermosensitive and electrically conducting properties. The polymerization of pyrrole took place directly inside the microgel networks, leading to formation of composite microgels and the morphology was observed by transmission electron microscope. PPy particles interacted strongly with microgels, as the acid groups of microgels acted as the polymeric codopant. The composite microgels thus formed showed electrically conducting behavior dependent on humidity and temperature. At temperatures lower than lower critical solution temperature, the conductivity decreased with increasing the humidity and a small hysteresis phenomenon was observed. The hysteresis became indistinct when temperature was near volume phase transition temperature. However, after the treatment of high temperature and high humidity, the conductivity increased surprisingly due to the structure reorganization inside the composite microgels. The distinctive functionality of the PPy composite microgels was expected to be utilized in many attractive applications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1648–1659, 2006     

Green synthesis of palladium nanoparticles using Hibiscus sabdariffa L. flower extract: Heterogeneous and reusable nanocatalyst in Suzuki coupling reactions

An elementary and ecological method has been designed for the biosynthesis of palladium nanoparticles, through the utilization of aqueous extract of red tea (Hibiscus sabdariffa L.) as a reducing and stabilizing agent. The nanoparticles obtained were characterized through UV–visible spectroscopy, transmission election microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, scanning election microscopy, energy‐dispersive X‐ray analysis and inductively coupled plasma analysis. The nanoparticles with spherical shape and dimensions of approximately 10 nm were used as a heterogeneous catalyst for Suzuki coupling reactions under mild conditions. The high efficiency of the catalytic reaction was affirmed by the good yields of products, easy work‐up, absence of palladium leached from the support and smooth recovery of catalyst.     

Temperature-Responsive Poly(N-Isopropylacrylamide-Acrylamide-Phenylboronic Acid) Microgels for Stabilization of Silver Nanoparticles

Poly(N-isopropylacrylamide-acrylamide-phenylboronic acid) [P(NIPAM-AAm-PBA)] microgels of uniform size were prepared by the chemical reaction of 3-aminophenylboronic acid with poly(N-isopropylacrylamide-acrylamide-acrylic acid) [P(NIPAM-AAm-AA)] microgels in aqueous medium in the presence of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride catalyst via carbodiimide coupling. Silver (Ag) nanoparticles were prepared using seed-mediated growth method and stabilized in P(NIPAM-AAm-PBA)] microgels. Ag nanoparticles and hybrid microgels were characterized by transmission electron microscopy, UV–visible, and dynamic light scattering techniques. The temperature-responsive behavior of hybrid microgels was found to be similar to that of the pure microgels. The value of volume transition temperature of hybrid microgels was found to be slightly higher than that of pure microgels due to shielding effect of Ag nanoparticles present on the surface of microgel particle. The decrease in the size of hybrid microgels as compared to that of pure microgels in swollen state is due to physical cross-linking by Ag nanoparticles inside the network of microgels. The stable hybrid polymer microgel system has a potential to be used for different applications.     

Palladium nanoparticles supported on mesoporous natural phosphate: An efficient recyclable catalyst for nitroarene reduction

We report the preparation of palladium nanoparticles supported on mesoporous natural phosphate (Pd@NP) using a wetness impregnation method. The prepared catalyst was characterized using various techniques. Furthermore, the reduction and preparation of the palladium nanoparticles was followed using UV–visible spectra. Based on the Scherrer equation, the crystallite size of the as‐synthesized palladium nanoparticles was 10.88 nm. The performance of the synthesized catalyst was investigated in the reduction of 4‐nitrophenol as a model substrate to 4‐aminophenol using NaBH₄ as a hydrogen source. Moreover, catalytic reduction of various nitroarenes was studied and monitored using UV–visible spectroscopy and gas chromatography. The Pd@NP catalyst showed a high activity for the selected reaction and could be recycled.