Poly(vinylpyridine) core/poly(N-isopropylacrylamide) shell microgel particles: their characterization and the uptake and release of an anionic surfactant

The use of microgel particles for controlled uptake and release of active species has great potential. The compatibility of microgel particles with their environment and the functionality of the particles can be achieved by modification of the core microgel through the addition of a shell. In this work, core-shell microgel particles, with a pH-responsive core (polyvinylpyridine) and a temperature-responsive shell (poly-N-isopropylacrylamide), have been prepared and characterized. The uptake and release of an anionic surfactant from the microgels has been investigated as a function of solution pH and temperature. The results indicate that electrostatic attraction between the anionic surfactant and the cationically charged core of the microgel particles is the dominant mechanism for absorption of the surfactant into the core-shell microgel particles.     

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．     

Particulate and continuum mechanics of microgel pastes: effect and non-effect of compositional heterogeneity

Microgels are deformable colloids that can be packed by external compression; such packing transforms a suspension of loose microgels into a viscoelastic paste with mechanical properties controlled by the elasticity of the constituent particles. We aim to understand how the presence of microgel particles with different individual elastic moduli affects this interplay in heterogeneous microgel packings. We do this by preparing microgel pastes that contain both soft, loosely cross-linked and stiff, densely cross-linked microgel particles and probe their shear elasticity. We consider particle packing fractions that cover the range from particles at the onset of contact to particles that are strongly packed, deformed, and deswollen to investigate the transition from a particulate suspension to a macrogel-type system. These studies reveal that the elasticity of heterogeneous microgel suspensions at low packing is due to the response of the soft, easily deformable microgel particles alone, whereas at high packing both soft and stiff microgels linearly add to the paste elasticity. This fundamental difference is due to the fundamentally different origin of elasticity at different microgel packing; whereas the soft particle interaction potential dominates the suspension mechanics at low microgel packing, rubber-like elasticity that equally reflects both soft and stiff contributions governs the mechanics of the same samples at high microgel packing.     

Swelling and deswelling of adsorbed microgel monolayers triggered by changes in temperature, pH, and electrolyte concentration

The formation and characterization of close-packed monolayers of negative, poly(N-isopropylacrylamide)-based microgel particles onto positively charged silicon wafers is described. The silicon wafers were rendered positive by first oxidizing their surface to silica and then adsorbing a layer of poly(ethyleneimine). The thickness of the deposited microgel monolayers (under aqueous conditions) has been determined by spectroscopic ellipsometry as a function of temperature (20-60 degrees C), pH (3-8), and added NaCl concentration (0-1 M). No actual desorption of the microgel particles was evident on changing the conditions, but a swelling/deswelling transition was observed around 32 degrees C. The thickness of the monolayer has been compared with the hydrodynamic diameter of the free microgel particles, dispersed in aqueous solution. For the poly(N-isopropylacrylamide) microgel particles, without any bulk ionisable comonomer groups present, the temperature dependence of the ellipsometric thickness of the monolayer mirrors closely that of the hydrodynamic diameter of the free particles. When ionizable (-COOH) groups are introduced into the microgel particles, however, this correspondence is largely lost because the microgel particles forming the deposited monolayer now contract strongly onto the oppositely charged substrate surface.     

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     

Absorption of cetylpyridinium chloride into poly(N-isopropylacrylamide)-based microgel particles, in dispersion and as surface-deposited monolayers

The addition of cetylpyridinium chloride (CPC) to aqueous dispersions of poly(N-isopropylacrylamide) [poly(NIPAM)] and poly(N-isopropylacrylamide-co-acrylic acid) [poly(NIPAM-co-AAc)] microgel particles leads to absorption of the CPC into the particles and to corresponding changes in their hydrodynamic diameter. With the latter set of particles there is a strong pH dependence. The dependence of both hydrodynamic diameter and electrophoretic mobility of the microgel particles on the added CPC concentration show a strong correlation with CPC uptake, as obtained from direct CPC absorption measurements. Various mechanisms for CPC absorption into the microgel particles are postulated, including electrostatic, polar, and hydrophobic interactions. A comparison has also been made between the effect of added CPC on the hydrodynamic diameter of free microgel particles in dispersion, determined by dynamic light scattering, and the thickness of adsorbed monolayers of the same microgel particles deposited on cationically modified, oxidized silicon surfaces, as determined from ellipsometry measurements. The trends observed in both cases are broadly similar. This work opens the way for development of microgel layers for controlled uptake and release applications.     

Preparation of Responsive Micrometer‐Sized Microgel Particles with a Highly Functionalized Shell

We describe a facile approach for the synthesis of micrometer‐sized (∼3.5 μm), pH‐responsive microgel particles, which have functional carboxylic acid groups concentrated in the shell. The large size offers the possibility to directly study the interactions between individual, isolated microgel particles with active ingredients by optical microscopy. Our results show that the synthesized microgel particles can load and release active ingredients via changing pH values. The complexation of Ca²⁺ with the ‐COOH functional groups located at the microgel surfaces not only regulates the active ingredient's uptake efficiency, but also provides a novel way to reveal the spatial distribution of the functional groups inside the microgel particles.     

含铅聚合物微凝胶与硫化氢反应前后在良溶剂中的分子扩散行为

用溶液聚合法制备出轻度交联的含铅微凝胶,用光子相关光谱技术测定其在良溶剂中与H2S反应前、后的扩散行为,由外推法得到在浓度无限稀时的分子扩散系数,给出微凝胶的流体力学半径。结果表明:相同量的含铅微凝胶在不同的初始浓度下与H2S反应,生成含PbS纳米微粒的凝胶；但其体积增大不同,这说明H2S与含铅微凝胶的反应既可以在分子内也可以在分子间进行,分子间的反应使含硫化铅微凝胶扩散系数随浓度的变化曲线的线性范围变小。     

Interaction of nonionic surfactants with copolymer microgel particles of NIPAM and acrylic acid

Binding of the nonionic surfactants Triton X-100 and Triton X-405 onto linear copolymers of N-isopropylacrylamide (NIPAM) and acrylic acid and to cross-linked microgel particles of similar composition but differing in their cross-link densities has been studied. The binding capacities vary for each of these polymeric systems, being smallest for the linear copolymer. The binding is also significantly less in all cases for the more hydrophilic surfactant, namely, Triton X-405. By comparing estimates of the pore or "cage" size within the microgel particles with the dimensions of the free micelles in solution, it is concluded that micelles of Triton X-100 form within the microgel particles more readily for the lower cross-linked microgel particles. However, micelles do not form as easily inside either microgel for Triton X-405. The swelling/deswelling behavior of each of the two microgels, in the presence of the surfactants, has been explained in terms of their relative binding behavior and how this contributes to the osmotic pressure difference inside and outside the microgel particles and also in terms of micelle "bridging" of the polymer network, causing shrinkage.     

Distribution of CdSe quantum dots within swollen polystyrene microgel particles using confocal microscopy

CdSe quantum dots (QDs) are semiconducting nanoparticles that fluoresce when stimulated by visible light. This property has been exploited in their use as tracer particles in biomedical applications. In this study, confocal microscopy has been used to determine the distribution of QDs within polystyrene microgel particles, dispersed in an organic solvent. It was found that the extent of microgel swelling affected the penetration of the QDs into the particles. Only when the microgel particles were swollen to their maximum extent were the QDs able to penetrate into the central core region of the particles.     

含铅聚合物微凝胶与硫化氢反应前后在良溶剂中的分子扩散行为

用溶液聚合法制备出轻度交联的含铅微凝胶,用光子相关光谱技术测定其在良溶剂中与H₂S反应前、后的扩散行为,由外推法得到在浓度无限稀时的分子扩散系数,给出微凝胶的流体力学半径。结果表明:相同量的含铅微凝胶在不同的初始浓度下与H₂S反应,生成含PbS纳米微粒的凝胶;但其体积增大不同,这说明H₂S与含铅微凝胶的反应既可以在分子内也可以在分子间进行,分子间的反应使含硫化铅微凝胶扩散系数随浓度的变化曲线的线性范围变小。     

Interpolyelectrolyte reaction between the particles of oppositely charged microgels

Processes that take place in oppositely charged microgel particles were studied. It was shown that water-swollen microgel particles about 100 μm in size were capable of interacting in dilute and concentrated dispersions to produce continuous dispersed systems. This interaction is accompanied by the release of water and low-molecular-mass counterions of network polyelectrolytes. Their liberation is due to the interpolyelectrolyte reaction between peripheral regions of unlike charged microgel particles in the particle contact zone.     

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.     

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.     

Photoresponsive surfactants in microgel dispersions

Microgel particles are cross-linked polymer particles. When dispersed in a good solvent for the polymer concerned, they are able to respond to a range of external stimuli by changing volume. Hence, microgel particles are suited to numerous applications (for example, controlled uptake and release) in the pharmaceutical, coatings, and water treatment industries. In this work, pH-sensitive, 0.5 wt % cross-linked poly(2-vinylpyridine) (PVP) microgel particles have been prepared and characterized. When the dispersion pH is decreased below 4.5, the pyridine groups become protonated and the microgel network becomes positively charged, causing the particles to expand. To investigate the possibility of using light as a trigger for effecting volume changes, the interaction of these microgel particles with a photodegradable anionic surfactant, 4-hexylphenylazosulfonate (C(6)PAS), has been investigated using dynamic light scattering and electrophoretic mobility measurements. The electrostatic attraction between the positively charged microgel network (at solution pH 3) and the negatively charged headgroups on the surfactant molecules caused a dramatic decrease in particle volume, and charge-reversal of the particles occurred with increasing surfactant concentration. The UV irradiation of phenylazosulfonate surfactants destroys the anionic headgroup of the molecules, and the microgel particles re-swell. The irradiation of PVP dispersions in the presence of C(6)PAS, along with mixed surfactant systems of sodium dodecyl sulfate plus C(6)PAS, has been investigated.     

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.     

Thermo-responsive behavior and microenvironments of poly(N-isopropylacrylamide) microgel particles as studied by fluorescent label method

Poly(N-isopropylacrylamide) (PNIPAM) microgel particles labeled with a fluorescent monomer 4-N-(2-acryloyloxyethyl)-N-methylamino-7-N,N-dimethylaminosulfonyl-2,1,3-benzoxadiazole (DBD-AE) were prepared by emulsion polymerization under various crosslinker concentrations. The thermo-responsive behavior and the microenvironment of the microgel particles were studied in water by turbidimetric and fluorescence analyses. For the microgel particles prepared under the crosslinker concentration of 1 mM, the turbidity began to increase at ca. 32.5 degrees C, but the relative fluorescence intensity dramatically increased and the wavelength at the maximum fluorescence intensity (lambda(max)) was dramatically blue-shifted both at ca. 31.5 degrees C with increasing the temperature, suggesting the hydrophobicity around the DBD-AE unit was dramatically increased and the subsequent shrinking of the microgel particles occurred. As the crosslinker concentration increased from 0.5 to 20 mM, the transition temperature determined by turbidimetric analysis was constant upto 2 mM, rose between 2 and 10 mM, leveled off above 10 mM, and was ca. 34 degrees C at 20 mM. The temperature-induced microenvironmental change inside the microgel particles was also reduced at high crosslinker concentrations. The results obtained from the fluorescence of the DBD-AE unit and another fluorescent monomer unit 3-(2-propenyl)-9-(4-N,N-dimethylaminophenyl)phenanthrene (VDP) suggested that the heterogeneity inside the microgel particles prepared under the crosslinker concentration of 20 mM became high.     

Microgel Capsules Tailored by Droplet‐Based Microfluidics

Microgel capsules are micrometer‐sized particles that consist of a cross‐linked, solvent‐swollen polymer network complexed with additives. These particles have various applications, such as drug delivery, catalysis, and analytics. To optimize the performance of microgel capsules, it is crucial to control their size, shape, and content of encapsulated additives with high precision. There are two classes of microgel‐capsule structures. One class comprises bulk microcapsules that consist of a polymer network spanning the entire particle and entrapping the additive within its meshes. The other class comprises core–shell structures; in this case, the microgel polymer network just forms the shell of the particles, whereas their interior is hollow and hosts the encapsulated payload. Both types of structures can be produced with exquisite control by droplet‐based microfluidic templating followed by subsequent droplet gelation. This article highlights some early and recent achievements in the use of this technique to tailor soft microgel capsules; it also discusses applications of these particles. A special focus is on the encapsulation of living cells, which are very sensitive and complex but also very useful additives for immobilization within microgel particles.     

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.