Composite Microgels Research Articles

Intestinal-targeted nanotubes-in-microgels composite carriers for capsaicin delivery and their effect for alleviation of Salmonella induced enteritis

Salmonella is a word-wide food-borne pathogen, which can cause severe enteritis and intestinal microbiota imbalance. Capsaicin (Cap), a food-based bioactive ingredient, has antibacterial and anti-inflammatory properties. However, its low solubility, low bioavailability and the irritation to digestive tract greatly limit its applications. Here, an intestinal responsively “nanotubes-in-microgel” composite carrier was constructed by capturing α-lactalbumin (α-lac) nanotubes in low-methoxy pectin microgels (LMP-NT) (52 μm). Cap was loaded in such system via hydrophobic interaction with a loading capacity of 38.02 mg/g. The LMP microgels remained stable and protected NT/Cap from early releasing in the gastric condition. It showed an excellent mucoadhesive capacity, which can prolong the intestinal retention up to 12 h and control release NT/Cap in intestine. Afterward, NT/Cap could penetrate across the mucus layer deeply and enter the intestinal villi epithelial cells efficiently. LMP-NT microgels achieved a mucoadhesive-to-penetrating transition in response to intestinal pH, improving the epithelium absorption and the in vivo bioavailability of Cap. Oral administration of LMP-NT/Cap could effectively alleviate enteritis caused by Salmonella infection and maintain the homeostasis of gut microbiota. Overall, this work suggested that LMP-NT composite microgels were promising for intestine-targeted and oral delivery of hydrophobic bioactive food compounds.

Fast-Curing Injectable Microporous Hydrogel for In Situ Cell Encapsulation.

Injectable hydrogels have previously demonstrated potential as a temporary scaffold for tissue regeneration or as a delivery vehicle for cells, growth factors, or drugs. However, most injectable hydrogel systems lack a microporous structure, preventing host cell migration into the hydrogel interior and limiting spreading and proliferation of encapsulated cells. Herein, an injectable microporous hydrogel assembled from gelatin/gelatin methacryloyl (GelMA) composite microgels is described. Microgels are produced by a water-in-oil emulsion using a gelatin/GelMA aqueous mixture. These microgels show improved thermal stability compared to GelMA-only microgels and benefit from combined photopolymerization using UV irradiation (365 nm) in the presence of a photoinitiator (PI) and enzymatic reaction by microbial transglutaminase (mTG), which together enable fast curing and tissue adhesion of the hydrogel. The dual-crosslinking approach also allows for the reduction of PI concentration and minimizes cytotoxicity during photopolymerization. When applied for in situ cell encapsulation, encapsulated human dermal fibroblasts and human mesenchymal stem cells (hMSCs) are able to rapidly spread and proliferate in the pore space of the hydrogel. This hydrogel has the potential to enhance hMSC anti-inflammatory behavior through the demonstrated secretion of prostaglandin E2 (PGE2) and interleukin-6 (IL-6) by encapsulated cells. Altogether, this injectable formulation has the potential to be used as a cell delivery vehicle for various applications in regenerative medicine.

Fabrication of poly (N-vinylcaprolactam-co-acrylic acid)-silver nanoparticles composite microgel with substantial potential of hydrogen peroxide sensing and catalyzing the reduction of water pollutants

Herein, we report the synthesis of poly(N- vinylcaprolactam-co-acrylic acid) microgel via free radical polymerization and its fabrication with silver nanoparticles. The fabricated microgels were applied for sensing and catalytic applications. The identification of functional groups in the pure and composite microgel was carried out by Fourier transform infrared spectroscopy. Dynamic laser light scattering studies confirmed the particulate nature of synthesized microgels with average diameter of ∼ 99 nm at pH 7. Thermal stability was checked with Differential Scanning Calorimetry and Thermogravimetric Analysis. X-ray diffraction pattern showed the amorphous nature of pure microgel, and face centered cubic geometry of incorporated AgNPs. The optical properties were evaluated by employing UV–visible spectroscopy. A clear observation of a red shift in the wavelength corresponding to localized surface plasmon resonance (λSPR) of AgNPs with a gradual increase in pH of medium ratified that the system is a potential candidate to be used as a pH sensor. The as-prepared composite microgel showed good sensing ability for hydrogen peroxide. Moreover, composite microgel was found to be an efficient catalyst for 4-Nitrophenol, 2-Nitrophenol and 2-Nitroaniline reduction to their respective amino compounds. Highest catalytic rate constant (kapp) by pseudo-first order kinetics was measured for 4-Nitrophenol as 1.03 min−1 at 323 K. In addition, fabricated composite microgel was also found to be a good catalyst for organic dyes, Methylene blue (MB) and Methyl Orange (MO) degradation.

Investigation of the 3D Printability of Covalently Cross-Linked Polypeptide-Based Hydrogels.

The 3D printability of poly(l-lysine-ran-l-alanine) and four-arm poly(ethylene glycol) (P(KA)/4-PEG) hydrogels as 3D biomaterial inks was investigated using two approaches to develop P(KA)/4-PEG into 3D biomaterial inks. Only the “composite microgel” inks were 3D printable. In this approach, P(KA)/4-PEG hydrogels were processed into microparticles and incorporated into a polymer solution to produce a composite microgel paste. Polymer solutions composed of either 4-arm PEG-acrylate (4-PEG-Ac), chitosan (CS), or poly(vinyl alcohol) (PVA) were used as the matrix material for the composite paste. The three respective composite microgel inks displayed good 3D printability in terms of extrudability, layer-stacking ability, solidification mechanism, and 3D print fidelity. The biocompatibility of P(KA)/4-PEG hydrogels was retained in the 3D printed scaffolds, and the biofunctionality of bioinert 4-PEG and PVA hydrogels was enhanced. CS-P(KA)/4-PEG inks demonstrated excellent 3D printability and proved highly successful in printing scaffolds with a narrow strand diameter (∼200 μm) and narrow strand spacing (∼500 μm) while the integrity of the vertical and horizontal pores was maintained. Using different needle IDs and strand spacing, certain physical properties of the hydrogels could be tuned, while the 3D printed porosity was kept constant. This included the surface area to volume ratio, the macropore sizes, and the mechanical properties. The scaffolds demonstrated adequate adhesion and spreading of NIH 3T3 fibroblasts seeded on the scaffold surfaces for 4 days. Consequently, the scaffolds were considered suitable for potential applications in wound healing, as well as other soft tissue engineering applications. Apart from the contribution to new 3D biomaterial inks, this work also presented a new and facile method of processing covalently cross-linked hydrogels into 3D printed scaffolds. This could potentially “unlock” the 3D printability of biofunctional hydrogels, which are generally excluded from 3D printing applications.

Link between Morphology, Structure, and Interactions of Composite Microgels.

We combine small-angle scattering experiments and simulations to investigate the internal structure and interactions of composite poly(N-isopropylacrylamide)–poly(ethylene glycol) (PNIPAM–PEG) microgels. At low temperatures the experimentally determined form factors and the simulated density profiles indicate a loose internal particle structure with an extended corona that can be modeled as a starlike object. With increasing temperature across the volumetric phase transition, the form factor develops an inflection that, using simulations, is interpreted as arising from a conformation in which PEG chains are incorporated in the interior of the PNIPAM network. This gives rise to a peculiar density profile characterized by two dense, separated regions, at odds with configurations in which the PEG chains reside on the surface of the PNIPAM core. The conformation of the PEG chains also have profound effects on the interparticle interactions: Although chains on the surface reduce the solvophobic attraction typically experienced by PNIPAM particles at high temperatures, PEG chains inside the PNIPAM network shift the onset of attractive interaction at even lower temperatures. Our results show that by tuning the morphology of the composite microgels, we can qualitatively change both their structure and their mutual interactions, opening the way to explore new collective behaviors of these objects.

Composite Microgels for Imaging-Monitored Tracking of the Delivery of Vascular Endothelial Growth Factor to Ischemic Muscles.

Monitoring the supply of vascular endothelial growth factor (VEGF) to ischemic tissues provides information on its biodistribution and delivery to meet the requirements of therapeutic angiogenesis and tissue engineering applications. We herein report the use of microfluidically generated microgels containing VEGF-conjugated fluorescent carbon dots (CDs) (VEGF-CDs), a gelatin-phenol conjugate, and silk fibroin for imaging-monitored tracking of VEGF delivery to ischemic muscles. An in vitro release study and a bioactivity assay indicated that the VEGF-CDs were released in a sustained manner with high bioactivity. The microgels showed a high angiogenesis potential, along with a strong fluorescent signal, for the chicken chorioallantoic membrane and chick embryo. Imaging and studies of therapeutic modalities of the composite microgels indicated their effective localization in ischemic tissues and sustained VEGF release, which resulted in enhanced therapeutic angiogenesis of ischemic muscles. This work reveals the success of using VEGF-loaded composite polymer microgels for efficient and monitored VEGF delivery by intramuscular administration for ischemic disease treatment.

Antibacterial, antioxidant and biocompatible nanosized quercetin-PVA xerogel films for wound dressing

Topical use of antimicrobial agents to treat wounds to inhibit bacterial invasion and facilitate wound healing is an effective strategy. In this work, an antibacterial xerogel film for potential applications in wound dressings was developed. First, a natural antibacterial agent, quercetin (Qu), was made into water-soluble quercetin-borate (QuB) nanoparticles by merging a solvent exchange method with the borate esterification reaction. QuB nanoparticles were then employed as the cross-linking agent to achieve gelation of poly(vinyl alcohol) (PVA) to obtain antimicrobial QuB-PVA composite microgels. Furthermore, QuB-PVA microgels were utilized as raw materials to produce xerogel films via an electrospray technique. The as-prepared QuB-PVA xerogel films exhibited excellent bacteriostasis, antioxidation, biocompatibility, self-healing, accelerated skin regeneration and functional restoration, and promoted skin wound healing. The QuB-PVA films significantly facilitated the in vivo healing speed of full-thickness skin wounds compared to commercial dressings. We believe that the present multifunctional QuB-PVA xerogel film is an excellent candidate for the wound dressings.

Swelling of composite microgels with soft cores and thermo-responsive shells

This study deals with constitutive modeling and numerical simulation of equilibrium swelling of composite microgels with soft temperature-insensitive cores and thermo-responsive (TR) shells. Our analysis takes into account a pronounced increase in the elastic moduli of TR gels of the LCST (lower critical solution temperature) type driven by aggregation of hydrophobic segments into clusters above the volume phase transition temperature. Material parameters are found by fitting observations on poly(acrylamide) and poly(N-isopropylacrylamide) gels with various concentrations of cross-linkers. Good agreement is demonstrated between the experimental data and results of numerical analysis. The effects of mechanical properties of the core and the shell and geometry of composite microgels on distribution of water molecules are studied numerically. Several unexpected phenomena are discovered in simulation.

Evaluation of alginate-biopolymers (protein, hydrocolloid, starch) composite microgels prepared by the spray aerosol technique as a carrier for green tea polyphenols

Effects of low methoxyl pectin, milk protein concentrate (MPC), and waxy starch on the encapsulation of green tea-polyphenols in alginate gels produced using spray aerosol technique were evaluated. MPC and waxy starch treated first by cold-renneted induced gelation method and gelatinization method, respectively. DSC thermal analysis and FTIR spectroscopy were used to prove the presence of polyphenols in gel matrixes. The encapsulation efficiency (%EE) and the polyphenols release were investigated using Folin-Ciocalteu assay. The results showed that the addition of biopolymers into alginate gels increased the encapsulation efficiency (%EE) but reduced the release percentage of polyphenol in water and simulated gastric fluid (SGF). Among the three biopolymers, cold-renneted MPC gave the best protection for polyphenols encapsulated in alginate microgels. It increased %EE from 63% to 68% in fresh gels, reduced the release percentage in water from 72% to 62% and reduced the release percentage in SGF from 76% to 67%.

Magnetic nanoparticles (Fe3O4 NPs) fabricated composite microgels and their applications in different fields

Abstract This article encircles the research progress of Fe3O4 NPs loaded composite microgel particles. Preparation methodologies, properties and applications of Fe3O4 NPs loaded composite microgel particles are elaborated here. The effect of different factors on the stability and tunable properties of Fe3O4 NPs loaded composite microgel particles was also investigated in detail. These composite particles have exceptional magnetic properties that make them demanding composite nano-formulation in different fields. Applications of these composite microgel particles in different fields as micro-reactor, drug delivery vehicles, and in adsorption and catalysis have also been elaborated in detail. These composite microgel particles can easily be recovered from the reaction mixture by applying an external magnet due to the presence of fabricated Fe3O4 NPs.

Facile fabrication of superhydrophobic surface with palygorskite-poly(2-(perfluorohexyl)ethyl methacrylate) composite microgels

To fabricate a superhydrophobic coating with fluorocarbon polymers, the substrate surface should be usually etched to produce a certain surface roughness. Here, the palygorskite-poly(2-(perfluorohexyl)ethyl methacrylate) (Pal-PFOL) composite microgels were designed via the radical polymerization of 2-(perfluorohexyl)ethyl methacrylate (FOL) in presence of the vinyl-modified palygorskite (V-Pal) nanorods as crosslinkers. After coating a mixed system containing an optimized ratio of the Pal-PFOL composite microgels and the free PFOL with a polymerPFOL/Pal-PFOL ratio of 1:4, a superhydrophobic surface was obtained with a static water contact angle (CA) of 153.6° on the polished single-crystal silicon (Si-100) wafer. The proposed strategy is expected for the simple fabrication of superhydrophobic surface on various substrates without etching treatment.

Synthesis of photocrosslinkable hydrogels for engineering three-dimensional vascular-like constructs by surface tension-driven assembly.

Surface tension-driven assembly is a simple routine used in modular tissue engineering to create three-dimensional (3D) biomimetic tissues with desired structural and biological characteristics. A major bottleneck for this technology is the lack of suitable hydrogel materials to meet the requirements of the assembly process and tissue regeneration. Identifying specific requirements and synthesizing novel hydrogels will provide a versatile platform for generating additional biomimetic functional tissues using this approach. In this paper, we present a novel composite hydrogel system based on methacrylated gelatin and γ-polyglutamic acid by UV copolymerization as the building block for fabricating vascular-like tissue via surface tension-driven assembly. The resulting composite hydrogels exhibited the improved mechanical properties and hydrophilicity, which greatly facilitate the assembly process. Subsequent cell encapsulation experiment proved that the hydrogel could provide 3D support for cellular spreading and migration. Furthermore, based on the composite microgel building blocks, cylindrical vascular-like construct with a perfusable microchannel was generated by the needle-assisted sequential assembly. In order to construct a biomimetic vascular tissue, the endothelial cells and smooth muscle cells were encapsulated in the microgels assembly with a spatial arrangement to build a heterogeneous double-layer tubular structure and the cells could readily elongate and migrate in the hollow concentric construct over 3days. These data suggest that this composite hydrogel is an attractive candidate for surface tension-driven assembly purposes, making the hydrogel potentially applicable in the fabrication of biomimetic vascularized tissues.

Core‐shell microgel stabilized silver nanoparticles for catalytic reduction of aryl nitro compounds

Silver nanoparticles loaded into shell of poly (styrene‐N‐isopropylmethacrylamide‐co‐acrylic acid) core shell [P (SNA‐CS)] gel particles were synthesized and analyzed by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), ultraviolet–visible spectroscopy (UV–vis) and dynamic light scattering (DLS). Catalytic activity of Ag@P (SNA‐CS) particles was investigated by reducing p‐nitroaniline (p‐NA) into p‐aminoaniline (p‐AA) in the presence of sodium borohydride (NaBH4) reductant. Molecules of the substrate adsorbed on the surface of silver nanoparticles interact with borohydride ions (BH4−) to form p‐AA. Other nitroarenes like o‐nitroaniline (o‐NA), p‐nitrophenol (p‐NP) o‐nitrophenol (o‐NP), 2,4‐dinitrophenol(2,4‐DNP) were also reduced into their corresponding aryl amines using Ag@P (SNA‐CS) composite microgels as catalyst. Reported catalyst efficiently reduced the nitro aromatic compounds individually as well as simultaneously at ambient temperature. Effect of different reaction conditions (catalyst dose, concentration of NaBH4 and concentration of p‐NA) on reaction completion time, value of apparent rate constant (kapp) and reduction efficiency of the catalyst for reduction of p‐NA was also demonstrated. Ag@P (SNA‐CS) catalyst was found to be able to retain activity up to four cycles.

One-pot HTST synthesis of responsive fluorescent ZnO@apo-enzyme composite microgels for intracellular glucometry.

Responsive fluorescent microgels, that can selectively, reversibly, and rapidly convert the fluctuation in intracellular glucose level into fluorescence signal, have the potential use for intracellular glucometry to promote the understanding of physiology. Herein, we report one-pot synthesis of such a responsive fluorescent composite microgels, which is made of a representative apo-enzyme, apo-glucose oxidase (apo-GOx), interpenetrated in a composite gel network that is comprised of ZnO quantum dots covalently bonded onto crosslinked poly(ethylene glycol) dimethacrylate. The key of this one-pot synthesis is applying a high-temperature short-time heating (HTST) method, so that the naturally dynamic profile of apo-GOx can be maintained and harnessed on the composite microgels to allow the highly selective response to glucose over a glucose concentration range of 0–20 mM. While the composite microgels can undergo volume phase transitions and convert both an increase and a decrease in glucose concentration into fluorescence signal shortly (<1 s), the changes in average hydrodynamic diameter and fluorescence of the composite microgels can be fully reversible even after twenty cycles of adding/removing glucose, indicating a reversible and rapid time response to the glucose concentration variations. With the composite microgels as biosensors, the fluorescence of the composite microgels embedded in the model cancer cells B16F10 can be modulated in response to intracellular glucose level variations, which are derived from a change in glucose concentration in the culture medium by an external supply, or that can be triggered by biochemical reactions (with the β-galactosidase catalysed hydrolysis of lactose as a model reaction for achieving increased glucose levels, and the GOx catalysed oxidation of glucose for achieving decreased glucose levels).

Effects of charge contrast and composition on microgel formation and interactions with bacteria-mimicking liposomes

Microgels offer opportunities for improved delivery of antimicrobial peptides (AMP). To contribute to a foundation for rational design of such systems, we here study the effects of electrostatics on the generation of peptide-carrying microgels. For this, alginate microgels loaded with polymyxin B and cross-linked by Ca2+, were formed by electrostatic complexation using a hydrodynamic focusing three-dimensional (3D)-printed micromixer, varying pH and component concentrations. The structure of the resulting composite nanoparticles was investigated by small-angle X-ray scattering, dynamic light scattering, and z-potential measurements, whereas peptide encapsulation and release was monitored spectrophotometrically. Furthermore, membrane interactions of these systems were assessed by dye leakage assays in model lipid vesicles. Our results indicate that charge contrast between polymyxin B and alginate during microgel formation affects particle size and network dimensions. In particular, while microgels prepared at maximum polymyxin B-alginate charge contrast at pH 5 and 7.4 are characterized by sharp interfaces, those formed at pH 9 are characterized by a more diffuse core, likely caused by a weaker peptide-polymer affinity, and a shell dominated by alginate that shrinks at high CaCl2 concentrations. Quantitatively, however, these effects were relatively minor, as were differences in peptide encapsulation efficiency and electrolyte-induced peptide release. This demonstrates that rather wide charge contrasts allow efficient complexation and particle formation, with polymyxin B encapsulated within the particle interior at low ionic strength, but released at high electrolyte concentration. As a consequence of this, peptide-mediated membrane destabilization were suppressed by microgel incorporation at low ionic strength, but regained after microgel disruption. After particle disruption at high ionic strength, however, some polymyxin B was found to remain bound to alginate chains from the disrupted composite microgel particles, resulting in partial loss in membrane interactions, compared to the free peptide.

Stimuli responsive microgel containing silver nanoparticles with tunable optical and catalytic properties

Abstract In this work, poly (vinylcaprolactam-co-itaconic acid) microgel was prepared by free radical polymerization. Silver nanoparticles were prepared in synthesized microgel networks by in situ reduction of Ag+ ions, loaded in microgel from aqueous solution of AgNO3. The prepared microgel was characterized by Fourier transformation infra-red spectroscopy, UV-Visible spectroscopy, fluorescence spectroscopy, X-ray diffraction, laser light scattering, thermal gravimetric analysis, differential scanning calorimetry and transmission electron microscopy. Swelling behavior of microgel was studied as a function of temperature and pH. The microgel was found to be in swollen state at low temperature and basic medium while in collapsed state at high temperature and acidic medium. A slight decrease in swelling capacity of microgel was observed after the fabrication of silver nanoparticles. A decrease in the emission intensity and a red shift in surface plasmon resonance wavelength of silver nanoparticles was observed with pH induced swelling of microgel. Catalytic activity of the composite microgel was studied by using them as catalyst for the reduction of 4-nitrophenol, methyl orange and methylene blue. Effects of temperature and catalyst dose were also investigated. The reduction rates of 4-NP, MB and MO were found to be 0.859, 0.0528 and 0.167 min−1, respectively. The change in catalytic performance and shift in absorption maxima and emission intensity of composite microgel as a function of temperature and pH reveals that this system has potential to be used as tunable catalyst and optical sensor.

Anti-oxidant activity reinforced reduced graphene oxide/alginate microgels: Mesenchymal stem cell encapsulation and regeneration of infarcted hearts

Mesenchymal stem cell (MSC) transplantation is promising for repairing heart tissues post myocardial infarction (MI). In particular, paracrine effects of the transplanted MSCs have been highlighted to play major roles in heart regeneration by secreting multiple growth factors and immune-modulatory cytokines. Nevertheless, its therapeutic efficacy still remains low, which is strongly associated with low viability and activity of the transplanted stem cells, because the transplanted MSCs are exposed to high shear stress during injection and harsh environments (e.g., high oxidative stress and host immune reactions) post injection. In this study, we aimed to develop novel injectable MSC-delivery microgel systems possessing high anti-oxidant activities. Specifically, we encapsulated MSCs in graphene oxide (GO)/alginate composite microgels by electrospraying. To further enhance the anti-oxidizing activities of the gels, we developed reduced MSC-embedded GO/alginate microgels (i.e., r(GO/alginate)), which have the potential to protect MSCs from the abovementioned harsh environments within MI tissues. Our in vitro studies demonstrated that the MSCs encapsulated in the r(GO/alginate) microgels showed increased viability under oxidative stress conditions with H2O2. Furthermore, cardiomyocytes (CMs), co-cultured with the encapsulated MSCs in transwells with H2O2 treatment, showed higher cell viability and cardiac maturation compared to monolayer cultured CMs, likely due to ROS scavenging by the gels and positive paracrine signals from the encapsulated MSCs. In vivo experiments with acute MI models demonstrated improved therapeutic efficacy of MSC delivery in r(GO/alginate) microgels, exhibiting significant decreases in the infarction area and the improvement of cardiac function. We believe that our novel MSC encapsulation system with GO, alginate, and mild reduction, which exhibits high cell protection capacity (e.g., anti-oxidant activity), will serve as an effective platform for the delivery of stem cells and other therapeutic cell types to treat various injuries and diseases, including MI.

Composite Microgels Created by Complexation between Polyvinyl Alcohol and Graphene Oxide in Compressed Double-Emulsion Drops.

Microgels, microparticles made of hydrogels, show fast diffusion kinetics and high reconfigurability while maintaining the advantages of hydrogels, being useful for various applications. Here, presented is a new microfluidic strategy for producing polymer-graphene oxide (GO) composite microgels without chemical cues or a temperature swing for gelation. As a main component of microgels, polymers that are able to form hydrogen bonds, such as polyvinyl alcohol (PVA), are used. In the mixture of PVA and GO, GO is tethered by PVA through hydrogen bonding. When the mixture is rapidly concentrated in the core of double-emulsion drops by osmotic-pressure-driven water pumping, PVA-tethered GO sheets form a nematic phase with a planar alignment. In addition, the GO sheets are linked by additional hydrogen bonds, leading to a sol-gel transition. Therefore, the PVA-GO composite remains undissolved when it is directly exposed to water by oil-shell rupture. These composite microgels can be also produced using poly(ethylene oxide) or poly(acrylic acid), instead of PVA. In addition, the microgels can be functionalized by incorporating other polymers in the presence of the hydrogel-forming polymers. It is shown that the multicomponent microgels made from a mixture of polyacrylamide, PVA, and GO show an excellent adsorption capacity for impurities.

Synthesis of Photocatalytic Niobate Nanosheet/Polymer Composite Microgel Particles through Microfluidic Approach

Polydimethylacrylamide (PDMA) microgels and niobate nanosheet/PDMA composite microgels were fabricated by using a microfluidic device. Morphologies and sizes of the composite microgels were tuned by adjusting synthetic conditions such as viscosity of oil phases, hydrophilicity and concentration of surfactants, and flow rates of oil phase and water phase. Furthermore, it was found that the dispersion of nanosheets was better when the composite microgels were synthesized by photopolymerization compared to redox polymerization.

Synthesis of Silver Nanoparticles Loaded onto Polymer-Inorganic Composite Materials and Their Regulated Catalytic Activity.

We present a novel approach for the preparation of polymer-TiO2 composite microgels. These microgels were prepared by the in situ hydrolysis and condensation of titanium tetrabutoxide (TBOT) in a mixed ethanol/acetonitrile solvent system, using poly(styrene-co-N-isopropylacrylamide)/poly(N-isopropylacrylamide-co-methacrylic acid) (P(St-NIPAM/P(NIPAM-co-MAA)) as the core component. Silver nanoparticles (AgNPs) were controllably loaded onto the polymer-TiO2 composite microgels through the reduction of an ammoniacal silver solution in ethanol catalyzed by NaOH. The results showed that the P(St-NIPAM)/P(NIPAM-co-MAA)-TiO2 (polymer-TiO2) organic-inorganic composite microgels were less thermally sensitive than the polymer gels themselves, owing to rigid O–Ti–O chains introduced into the three-dimensional framework of the polymer microgels. The sizes of the AgNPs and their loading amount were controlled by adjusting the initial concentration of [Ag(NH3)2]+. The surface plasmon resonance (SPR) band of the P(St-NIPAM)/P(NIPAM-co-MAA)-TiO2/Ag (polymer-TiO2/Ag) composite microgels can be tuned by changing the temperature of the environment. The catalytic activities of the polymer-TiO2/Ag composite microgels were investigated in the NaBH4 reduction of 4-nitrophenol. It was demonstrated that the organic-inorganic network chains of the polymer microgels not only favor the mass transfer of the reactant but can also modulate the catalytic activities of the AgNPs by tuning the temperature.