Thermosensitive particles

Keywords Hydroxyapatite Microgel Nanoparticles Thermosensitive particle... 

Hazot P, Delair T, Elaissari A, Chapel JP, Pichot C. Ennctionalization of poly(A-ethyhnethacrylamide) thermosensitive particles by phenylboronic acid. Colloid Polym. Sci. 2002 280 637-646. 

It turns out that in solutions of c < 0.1 gL 1 thermosensitive homopolymers, such as PNIPAM, PVCL, and PVME, themselves, form stable colloids in water at elevated temperature in the absence of additives or chemical modification [141-147]. The colloids remain stable upon prolonged heat treatment, without detectable aggregation or precipitation. Also, core-shell particles consisting of PNIPAM and a hydrophobic block are stable not only below but also above the LCST up to 50 °C, when the PNIPAM block is expected to be insoluble [185]. Factors that determine the colloidal stability as defined in Sect. 1.1 do not explain, it seems, their stability. In this review we have compiled a fist of all the reported instances where the formation of stable particles was detected in aqueous solutions of neutral thermosensitive neutral polymers at elevated temperature. We present studies of homopolymers, as well as their copolymers consisting of thermosensitive fragments and ei-... 

Thermosensitive microgel particles (Rh = 300-500 nm) were synthesised by electron beam irradiation of dilute aqueous PVME solutions [330]. It was noted that when the irradiation of the PVME solution (4.0g I, ) was... 

Suzuki, D. Kawaguchi, H., Modification of gold nanoparticle composite nanostructures using thermosensitive core shell particles as a template, Langmuir. 2005, 21, 8175 8179... 

Furthermore, Fu et al.140 developed a transport system that responds to thermal stimuli. This system is based on chains of poly-iV-isopropylacrylamide (a known thermosensitive polymer), which exists in a collapsed, hydrophobic state when exposed to heat, but in an expanded, hydrophilic state in the cold. In this way, samples of mesoporous, spherical silica particles (particle diameter 10 p,m) that were lined and coated with the thermosensitive polymer by atom transfer radical polymerization... 

Cruz-Silva R, Arizmendi L, Del Angel M et al (2007) pH- and thermosensitive polyaniline colloidal particles prepared by enzymatic polymerization. Langmuir 23 8-12... 

As an example, thermosensitive PVME microgels can be used as template and stabilizer for the synthesis of composite polypyrrole (PPy) particles [32], The PVME microgels were obtained by electron beam irradiation above the phase transition temperature as described in Sect. 3.2.1 [3,4], Pyrrole (Py) was polymerized by oxidative polymerization with ferric chloride in the presence of the PVME microgels in water/ethanol mixtures as reaction medium. For comparison, the synthesis was also carried out in the presence of uncross-linked PVME. 

Recently, core-shell type microgels, which contain a hydrophobic core and a hydrophilic thermosensitive shell, have become attractive for scientists because such systems can combine the properties characteristic of both the core and the shell [53], We have prepared core-shell microgel particles consisting of a poly(styrene) core onto which a shell of polyCA-isopropylacrylamide) (PS-PNIPA) has been affixed in a seeded emulsion polymerization [54-56], In this case, the ends of the crosslinked PNIPA chains are fixed to a solid core, which defines a solid boundary of the network. In this respect, these core-shell latex particles present crosslinked polymer brushes on defined spherical surfaces. The solvent quality can be changed from good solvent conditions at room temperature to poor solvent conditions at a temperature... 

Fig. 1 Volume transition in thermosensitive core-shell particles. The thermosensitive PNIPA networks are affixed to the surface of the core particles, and thus provide one boundary of the network. The solvent (water) is taken up by the network at low temperature, but is expelled when the shell undergoes a volume transition at 32°C...

Recently, we have successfully used these thermosensitive core-shell microgel particles as templates for the deposition of metal nanoparticles (Ag, Au, Pd, Pt, and Rh) [29, 59, 60], The reduction to metallic nanoparticles in the presence of microgel particles was done at room temperature via the addition of NaBPL and could be followed optically by the color change of the suspensions, as shown in Fig. 3. The immobilization of metal nanoparticles might be due to the strong localization of... 

Investigations by DLS measurements of composite particles indicated that the original thermosensitive properties of the PNIPA network are not suppressed by the incorporation of metal particles into the network. That is, the shrinking and re-swelling of microgel is not hampered by the incorporation of metal nanoparticles into the network. The metal composite particles show similar volume transition temperature as the carrier particle at 32°C, which is in excellent agreement with previous findings on these systems as shown in Fig. 7 [64, 65], This indicates... 

Fig. 8 Composite particles consisting of thermosensitive core-shell particles in which metallic nanoparticles are embedded. Left The composite particles are suspended in water, which swells the thermosensitive network attached to the surface of the core particles. In this state, the reagents can diffuse freely to the nanoparticles, which act as catalysts. Right At higher temperatures (T > 32°C) the network shrinks and the catalytic activity of the nanoparticles is strongly diminished...

In the meantime, this phenomenon has also been observed by other groups for thermosensitive polymer-based metal nanoparticles [77, 78]. Pich et al. have used microgel particles based on the copolymer of A-vinylcaprolactam (VCL) and ace-toacetoxyethyl methacrylate (AAEM) (PVCL/PAAEM) as the carrier system for the deposition of metal nanoparticles. The microgels were first modified with poly(3,4-ethylenedioxythiophene) (PEDOT) nanorods through an in situ oxidative polymerization process. Microgels with PEDOT nanorods in the shell were then used for the... 

Metal nanoparticles embedded in thermosensitive core-shell microgel particles can also work efficiently as catalyst for this reaction. Figure 13 shows the oxidation reaction of benzyl alcohol to benzaldehyde in aqueous media by using microgel-metal nanocomposite particles as catalyst. All reactions were carried out at room temperature using aerobic conditions. It is worth noting that the reaction conditions are very mild and no phase transfer catalyst is needed. It has been found that microgel-metal nanocomposites efficiently catalyze the aerobic oxidation of benzyl alcohol at room temperature. No byproducts have been detected by GC after the reaction, and water is the only product formed besides the aldehyde. 

Fig. 14 Catalytic oxidation of benzyl alcohol in the presence of metal nanoparticles immobilized in thermosensitive core-shell microgels at different temperatures. At lower temperatures (T < 32°C) the microgel network is hydrophilic and swollen in water, whereas at high temperatures (T > 32°C), the network shrinks and becomes hydrophobic. Thus, microgel particles embedding the metal catalyst will move to the oil phase, which will be favorable for the uptake of hydrophobic benzyl alcohol into the metal-microgel composite. Therefore, the catalytic activity of the metal-microgel composites will be affected both by the volume transition and the polarity change of the microgel [29]...

Thus, the results shown here demonstrate that thermosensitive microgel particles can serve as superior carriers for the adsorption of enzymes in which the activity of adsorbed enzymes are preserved. The catalytic activity of adsorbed P-D-glucosidase from almonds is increased by a factor of more than three. Moreover, the catalytic properties of immobilized enzymes can be manipulated by the volume transition of the microgel. Hence, such microgels present a novel class of active nanoreactors for biocatalysis. 

All results reviewed herein demonstrate that the microgel particles may serve as nanoreactors for the immobilization of catalytically active nanostructures, namely for metal nanoparticles and enzymes. In both cases, the resulting composites particles are stable against coagulation and can be easily handled. Moreover, the catalytic activity of metal nanoparticles can be modulated through the volume transition that takes place within the thermosensitive microgel carrier system. Similar behavior has been also observed for the temperature dependence of enzymatic activity. Thus, the microgel particles present an active carrier system for applications in catalysis. 

Dingenouts N, Norhausen Ch, Ballauff M (1998) Observation of the volume transition in thermosensitive core-shell latex particles by small-angle X-ray scattering. Macromolecules 31 8912-8917... 

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