Functionalization of cotton with poly-NiPAAm/chitosan microgel. Part I. Stimuli-responsive moisture management properties

Stimuli-responsive microgel, based on synthetic polymer (poly-NiPAAm) and biopolymer (chitosan), was incorporated onto cotton fabric surface by pad-dry-cure method using 1,2,3,4-butanetetracarboxylic acid (BTCA) as crosslinker. In order to assess the moisture management properties of cotton functionalized with responsive microgel, the effects of temperature, relative humidity and concentration of microgel on water vapour transmission rate (WVTR) and moisture content (MC) were quantified. Since the use of experimental design is considered as a highly attractive feature in dealing with experiments and variables of this nature, the effects were quantified by using a central composite design. The regression equations obtained from the statistical analysis allowed the prediction of WVTR and MC at different ambient conditions. Material properties such as crease recovery and whiteness were also measured. The results indicate that both relative humidity and temperature significantly influence studied responses (WVTR and MC), showing that good perspiration can be achieved at lower humidity levels and at higher temperatures. The observed phenomena are attributed to controlled expansion (or contraction) of the surface incorporated microgel, which acts as a sensor of temperature and as a valve to regulate the water vapour permeability of functionalized cotton.     

Sol–gel technology for functional finishing of PES fabric by stimuli-responsive microgel

The possibility of incorporating a stimuli-responsive microgel into a silica matrix by the sol–gel method was studied. This method allows the preparation of a novel class of functional finishes for textile material modification, which is aimed at the creation of simultaneous stimulus-responsive behaviour and functional protective properties. Using a pad-dry-cure method, a thermo- and pH-responsive microgel (PNCS) based on poly-(N-isopropylacrylamide) (poly-NiPAAm) and chitosan was embedded into a silica matrix on a previously activated polyester (PES) fabric. The matrix was composed of a model sol–gel precursor, vinyltrimethoxysilane (VTMS), in combination with hydrophilic fumed silica nanoparticles (SiO₂). Functionalized PES fabric samples were characterised by determining the morphological and chemical properties using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The stimuli (temperature and pH) responsiveness of the functionalized PES fabric was established by measuring its porosity, wicking ability, moisture content, drying rate, water vapour transmission rate and water uptake. In order to assess the washing fastness of the surface modifying systems, the tests were done before and after five consecutive washings. The results showed that sol–gel technology is an appropriate method for the incorporation of PNCS microgel on PES fibre surface. Because of the elasticity of the sol–gel matrix, the VTMS/SiO₂ polysiloxane film had no adverse influence on the swelling/deswelling effect of the PNCS microgel, thus retaining and even enhancing its stimulus response.     

Poly(N-vinylcaprolactam-co-glycidyl methacrylate) aqueous microgels labeled with fluorescent LaF3:Eu nanoparticles

We describe the synthesis and properties of functional microgel particles based on poly(N-vinylcaprolactam-co-glycidyl methacrylate) (PVCL/PGMA) copolymer. A series of colloidally stable microgel particles with a range of glycidyl methacrylate content were prepared by surfactant-free heterophase polymerization in water. The microgel particles obtained had hydrodynamic radii between 250 and 350 nm and were fairly monodisperse in size; however, a broadening of the particle size distribution was observed for samples with a low GMA content. The PVCL/PGMA microgel particles exhibit thermally responsive reversible changes in diameter in water, and the swelling degree increased with the PVCL fraction in the copolymer structure. These microgels were then modified with photoluminescent europium-doped lanthanum fluoride nanoparticles (LaF3:Eu-AEP) through reaction of the 2-aminoethyl phosphate surface ligands with epoxy groups present in the microgel. These hybrid microgels were colloidally stable and thermally responsive in aqueous solution.     

Use of functional microgels with vinyl groups to accelerate photopolymerization reaction

Three types of functional microgels with vinyl groups on their surface were prepared. For the first type, the counter anion from clorin was exchanged with β-methacryloylethyl sulfonic acid, styrene sulfonic acid or allyl sulfonic acid in a microgel with ammonium anions. For the second and third types, a quaternization with N,N-dimethylaminoethyl methacrylate of 3-chloro-2-hydroxypropyl methacrylate in the presence of microgel particles was prepared by emulsion copolymerization of styrene, chloromethylstyrene or N,N-dimethylamino-methylbenzene, and divinylbenzene. The resulting samples show good dispersibility in organic solvents without an emulsifier. A functional microgel-based photopolymer combined with an acrylate monomer and ultraviolet (UV) or visible (VIS) light-absorbing photoinitiators provides oleophilic images when exposed to UV or VIS light and developed in tap water. This photopolymer has a higher sensitivity than those of photopolymers based on microgels with an analogous composition but without vinyl groups. Photopolymers pepared by using functional microgels with a methacryloyl group exhibited a higher rate of polymerization (R_p) than that of photopolymers based on microgels without a vinyl group. The R_p of photopolymers prepared by using a functional microgel with either an allyl group or vinylphenyl group was nearly equal to that of photopolymers based on microgels with ammonium ions. Their high sensitivities are attributed to the rapid photopolymerization in the methacryloyl group. To determine how the photoreaction mechanism enhances sensitivity, the photoreaction products were investigated using a model photopolymerization system. It was found that the gelation reactions enhancing sensitivity are predominantly the polymerization and crosslinking ones when a microgel with the methacryloyl group is used, and the graft copolymerization with acrylate monomers when a microgel with either the allyl group or vinylphenyl group is used.     

Synthesis of Polyampholyte Janus-like Microgels by Coacervation of Reactive Precursors in Precipitation Polymerization

Controlling the distribution of ionizable groups of opposite charge in microgels is an extremely challenging task, which could open new pathways to design a new generation of stimuli-responsive colloids. Herein, we report a straightforward approach for the synthesis of polyampholyte Janus-like microgels, where ionizable groups of opposite charge are located on different sides of the colloidal network. This synthesis approach is based on the controlled self-assembly of growing polyelectrolyte microgel precursors during the precipitation polymerization process. We confirmed the morphology of polyampholyte Janus-like microgels and demonstrate that they are capable of responding quickly to changes in both pH and temperature in aqueous solutions.     

双敏性微凝胶的絮凝及聚沉行为

用沉降聚合法制备了聚(N-异丙基丙烯酰胺-co-甲基丙烯酸)微凝胶, 并用NMR, DLS分析测定了微凝胶结构及凝胶颗粒在不同离子强度下粒径和表面电势的变化. 25 ℃时在pH＝7的溶液中Zeta电位为－18 mV, 随离子强度增加, 逐渐减小. 当NaCl浓度达0.2 mol/L时基本不变, 表明微凝胶表面电荷受到屏蔽, 浓度继续增加主要使凝胶颗粒收缩. 加热引起微凝胶收缩, 颗粒表面电荷密度增大, Zeta电位增大. 在0.2 mol/L NaCl溶液中, 41 ℃时微凝胶的Zeta电位可达－12.4 mV, 使微凝胶稳定. 较高离子强度时, Zeta电位随温度升高发生突变, 微凝胶表面几乎为中性, 其突变温度与临界絮凝温度(CFT)相当. CFT随离子强度增加向低温迁移, 微凝胶聚集速率在高温时比低温时快.     

Preparation and characterization of pH‐responsive and thermoresponsive hybrid microgel particles with gold nanorods

We report on pH‐responsive and thermoresponsive hybrid materials based on the assembly of gold nanorods, Au NRs, into multiresponsive, crosslinked copolymer microgel particles. These microgel particles were prepared by the surfactant‐free emulsion polymerization of N‐isopropylacrylamide and acrylic acid using N, N′‐methylene bis‐acrylamide as a crosslinker, which produces particles measuring approximately 160 nm that are interconnected to one other. Cetyltrimethyl ammonium bromide‐stabilized Au NRs were also prepared independently using a seed‐mediated growth method and then loaded into swollen, deprotonated, acrylic acid‐containing microgel particles using the electrostatic interactions between the oppositely charged particles. Transmission electron micrographs of the as‐prepared hybrid Au NR–microgel particles confirmed that the Au NRs were attached to the surface of the microgel particles. The size‐dependent temperature‐responsive characteristics of the hybrid microgel particles were studied by dynamic light scattering, and it was found that as the temperature increased across the phase transition temperature, the particle size decreased to 56% of the original volume. The thermoresponsive and pH‐responsive optical properties of the hybrid microgel particles were also systematically investigated. The thermo‐ and pH‐induced shrinkage of the microgel led to an increase in the UV–vis absorption intensity and caused a significant blue shift in the longitudinal surface plasmon bands of the Au NRs. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Responsive hydrogel colloids: Structure,interactions, phase behavior,and equilibrium and nonequilibrium transitions of microgel dispersions

Soft and responsive colloids based on polymer hydrogels have moved into the focus of the colloid community. This review gives a brief overview of the recent literature on the structure and phase behavior of neutral and ionic poly(N-isopropylacrylamide) microgel dispersions from dilute to over-packed conditions, focusing in particular on the ability of these particles to adapt their size and shape in response to external stimuli. The review is hierarchical; it first covers the aspects of an individual microgel particle viz., the internal structure of inhomogeneous and homogeneously cross-linked particles, followed by studies of ensembles of particles covering in particular structural ordering, phase behavior, and liquid–solid and solid–solid transitions. Insights on the ability of the microgel particles to deform, compress, and interpenetrate beyond the close-packed volume fractions are discussed. Building complex architectures using microgel particles for fundamental studies as well as future applications is reviewed towards the end of the article.     

Dehumidification and humidification of air by surface-soaked liquid membrane module with triethylene glycol

A novel liquid membrane system, a surface-soaked liquid membrane, with triethylene glycol (TEG) on the hydrophilic-treated surface of the hydrophobic microporous membrane was developed and used for the dehumidification and humidification of air. The selectivity of the TEG liquid membrane for water vapor with respect to air was over 2000, which was derived from the selective absorption of the TEG liquid. A flat-type liquid membrane module with a dual membrane surface was designed, of which the TEG liquid membrane thickness was 18 μm and the permeation area was 0.13 m². The liquid membrane humidifier and dehumidifier consisted of the membrane module and a vacuum pump. As a dehumidifier, the membrane system recovered water vapor at 4.1 g/h from 70%RH room air at 298 K. For use as a humidifier, the air flow was effectively humidified by the permeated water vapor through the membrane module. The effects of the air humidity and sweep air flow rate were studied and discussed. Simple model calculations based on the permeability of the water vapor well predicted the experimental results.     

以微凝胶模板合成P(AM-co-DMC)/SiO_2杂化粒子

以聚(丙烯酰胺-co-甲基丙烯酰氧乙基三甲基氯化铵)[P(AM-co-DMC)]微凝胶为模板,TMOS为硅前驱体,中性水环境下合成了一系列P(AM-co-DMC)/SiO2有机-无机杂化粒子.对杂化粒子的大小、形态及表面形貌等进行研究,发现微凝胶对杂化粒子的形态和大小起主导作用,SiO2在模板上沉积,即使经过灼烧依然保持模板的形态;TMOS的用量对杂化粒子的性质也有重要影响——用量少时,得到的杂化粒子表面粗糙,增加用量会使表面变得光滑.杂化粒子经过灼烧后,表面会变得更加粗糙.     

Synthesis,Characterization, and Silver Nanoparticles Fabrication in N-isopropylacrylamide-Based Polymer Microgels for Rapid Degradation of p-Nitrophenol

Multiresponsive poly(N-isopropylacrylamide-co-methacrylic acid) microgels were synthesized by precipitation polymerization in aqueous medium. Then silver-poly(N-isopropylacrylamide-co-methacrylic acid) hybrid microgels were prepared by in-situ reduction of silver ions. Formation of microgels was confirmed by Fourier transform infrared spectroscopic analysis. pH and temperature sensitivity of microgel was studied by dynamic light scattering. Hydrodynamic radius of microgels decreases with increase in temperature at pH 8.20 and show volume phase transition temperature around 45°C. At pH 2.65, hydrodynamic radius decreases with increase in temperatures upto 35°C but further increase in temperature causes aggregation and microgel becomes unstable due to increase of hydrophobicity. With increase in pH of medium, the hydrodynamic radius of microgels increases sigmoidally. Formation of silver nanoparticles inside microgel and pH dependence of surface plasmon resonance wavelength of the hybrid microgels were investigated by ultraviolet-visible spectroscopy. The value of surface plasmon resonance band and absorbance associated with surface plasmon resonance band increases with increases in pH of the medium. The apparent rate constant of reduction of p-nitrophenol was found to be linearly dependent on volume of hybrid microgels used as catalyst. The system has a potential to be used as effective catalyst for rapid degradation of industrial pollutant.     

Preparation and characterization of poly (N-isopropylacrylamide)/polyvinylamine core-shell microgels

In this paper, well-defined temperature- and pH-sensitive core-shell microgels were synthesized by graft copolymerization in the absence of surfactant and stabilizer. The microgel particles consisted of poly (N-isopropylacrylamide (NIPAm)) core crosslinked with N, N′-methylene-bisacrylamide (MBA) and polyvinylamine (PVAm) shell. The effect of MBA content and NIPAm/PVAm ratio on microgel size was investigated. SEM showed that the microgels were spherical and had narrow particle-size distribution. TEM images of the microgels clearly displayed well-defined core-shell morphologies. Zeta-potential measurement further elucidated that the microgels possessed positively charged PVAm molecules on the microgel surface. Turbidity measurement and ¹H-nuclear magnetic resonance (NMR) experiments indicated that the VPTT of microgels was the same as the LCST of PNIPAm. ¹H-NMR experiments also inferred that the methyl proton of N-isopropylacrylamide appeared three peaks and responded to hydrogen-bonding interaction including polymer chain with water molecular, intramolecular interaction and intermolecular interaction, respectively.     

Hybrid microgels photoresponsive in the near-infrared spectral range

We report for the first time a photothermally responsive composite material based on polymer microgel particles doped with gold nanorods. We used the dependence of the longitudinal surface plasmon of the gold nanorods on their aspect ratio to synthesize nanoparticles with strong absorption in the near-IR spectral range (in the "water window"). The nanoparticles were incorporated in the interior of temperature-responsive poly(N-isopropylacrylamide-acrylic acid) microgels. Upon irradiation at lambda = 810 nm, hybrid microgel particles doped with Au nanorods underwent a strong deswelling phase transition. These photothermally responsive microgels can be used to carry and release small molecules (e.g., small protein molecules and drugs).     

Dynamic elasticity of films formed by poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) microparticles on a water surface

Surface dilatational dynamic elasticity ε of films formed by cross-linked poly(N-isopropylacrylamide) microparticles on a water/air interface has been determined as a function of polymer surface concentration Γ. The experimental dependences exhibit two maxima of ε at surface pressures π of nearly 6 and 35 mN/m. In the region of the second maximum, the pattern of the dependence is governed by a method used to vary Γ. At π > 25 mN/m, film compression leads to the formation of a metastable monolayer, while the gradual addition of a microparticle dispersion results in the establishment of equilibrium between the monolayer and surface aggregates. In the region of π values corresponding to the second maximum of ε, slow relaxation processes with a characteristic time substantially longer than 10 s occur in the system. At π > 35 mN/m, the film collapses due to the displacement of microgel particles from the water surface.     

pH‐triggerable and ultraviolet‐triggerable β‐cyclodextrin microgel

β‐Cyclodextrin (βCD) microgels were prepared water in oil emulsion, and cinnamic acid (CA) was loaded in the microgel by inclusion complexation. The specific loading of CA in the microgel was 0.0203 mg/mg, and it was less than that the calculated specific loading (0.0368 mg/mg). The maximum swelling ratio of CA‐loaded βCD microgel (CAβCD microgel) decreased from 233.9% to 225.7% upon the irradiation of ultraviolet light (λ = 365 nm). And the 5(6)‐carboxyfluorescein release of CAβCD microgel, observed for 12 h, was suppressed upon the irradiation of ultraviolet light, possibly because the microgel can be photocross‐linked, and its mass transfer resistance against dye diffusion would increase. The swelling ratio of CAβCD microgel somewhat depended on the pH value of the medium, possibly because electrostatic repulsion can be developed within the microgel by the ionizable carboxylic group of CA. The 5(6)‐carboxyfluorescein release degree in 12 h of CAβCD microgel increased from 10.5% to 85.1% when the pH value increased from 3.0 to pH 9.0. This is mainly because CA is more soluble at a higher pH value. In the full range of pH value tested, the release degrees of CAβCD microgel were slightly higher than those of βCD microgel, possibly because of the electrostatic repulsion developed within the CAβCD microgel. Copyright © 2014 John Wiley & Sons, Ltd.     

Cooperatively assembled liquid crystals enable temperature-controlled Förster resonance energy transfer

Balancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal–optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system. Indeed, FRET exhibits strong S-curve dependence as temperature sweeps through the liquid crystal phase transformation. Such thermochromic materials, suitable for dynamic thermo-optical sensing and modulation, are anticipated to unlock new and smart approaches for controlling and directing light in stimuli-responsive devices.

A temperature-sensitive Förster resonance energy transfer system was constructed using a highly emissive liquid crystal co-assembled with Nile red, enabling thermo-optical modulation for controlling and directing light in stimuli-responsive devices.     

聚(N-异丙基丙烯酰胺)水凝胶微球体积相变的研究

窄分散的聚（Ｎ 异丙基丙烯酰胺）水凝胶微球用乳液聚合方法制备，并用动态和静态光散射对其体积相变进行了研究．与水中聚（Ｎ 异丙基丙烯酰胺）线性单链比较，水中凝胶微球的体积相变温度较高，对温度的响应比较平缓．相变是连续的，有别于大块凝胶非连续的体积变化．在体积相变过程中，凝胶微球始终是密度均一的热力学稳定球体．从相变过程网络密度的变化可以确定，绝大部分的水在收缩过程被排了出来，但在紧缩的凝胶微球中仍含有约７０％的水．     

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     

Dynamic control of volume phase transitions of poly(N‐isopropylacrylamide) based microgels in water using hydrazide‐aldehyde chemistry

We demonstrate that the volume phase transition temperature (VPTT) of copolymer microgel particles made from N‐isopropylacrylamide (NIPAm) and methacryloyl hydrazide (MH) can be tailored in a reversible manner upon the reaction of the hydrazide functional groups with aldehydes. The microgels were synthesized by precipitation polymerization in water. Due to the water‐soluble nature of the MH monomer, the VPTT at which the microgel particles contract shifts to higher values by increasing the incorporated amounts of methacryloyl hydrazide from 0 to 5.0 mol %. The VPTT of the copolymer microgel dispersions in water can be fine‐tuned upon addition of hydrophobic/hydrophilic aldehydes, which react with the hydrazide moiety to produce the hydrazone analogue. This hydrazone formation is reversible, which allows for flexible, dynamic control of the thermo‐responsive behavior of the microgels. The ability to “switch” the VPTT was demonstrated by exposing hydrophilic streptomycin sulfate salt incubated microgel particles to an excess of a hydrophobic aldehyde, that is benzaldehyde. The temperature at which these microgels contracted in size upon heating was markedly lowered in these aldehyde exchange experiments. Transformation into benzaldehyde hydrazone derivatives led to assembly of the microgel particles into small colloidal clusters at elevated temperatures. This control of supracolloidal cluster formation was also demonstrated with polystyrene particles which had a hydrazide functionalised microgel shell. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1745–1754     

Swelling behavior of poly- N-isopropylacrylamide microgel particles in alcoholic solutions

 It has been shown that the swelling of poly-N-isopropyl-acrylamide (poly-NIPAM) microgel particles can be controlled by the addition of alcohols, in addition to the previously observed effect of temperature. The degree of swelling is also controlled by the amount of cross-linker within the microgel particles. At 25 ^°C, poly-NIPAM microgel particles collapse upon the addition of MeOH, EtOH and 2-PrOH to a minimum size and then, reswell again as the alcohol-rich region is approached. This trend was also observed for poly-NIPAM microgel particles dispersed in 2-PrOH/water mixtures upon heating to 50 ^°C. The particles, dispersed in either water or alcohol/water mixtures were found to be stable to flocculation between 25 ^°C and 50 ^°C. Received: 27 February 1997 Accepted: 5 August 1997