Copolymerization Kinetics of Dopamine Methacrylamide during PNIPAM Microgel Synthesis for Increased Adhesive Properties.

Combining stimuli-responsive properties of gels with adhesive properties of mussels is highly interesting for a large field of applications as, e.g., in life science. Therefore, the present paper focuses on the copolymerization of poly(N-isopropylacrylamide) (PNIPAM) microgels with dopamine methacrylamide (DMA). A detailed understanding of reaction kinetics is crucial to figure out an optimized synthesis strategy for tailoring microgels with adhesive properties. The present study addresses the influence of relevant synthesis parameters as the injection time of DMA during the microgel synthesis and the overall reaction time of the microgel. Reaction kinetics were studied by mass spectrometry of time samples taken during the microgel synthesis. This allowed us to determine the monomer consumption of NIPAM, the cross-linker N,N'-methylenebisacrylamide (BIS), and DMA. A second-order reaction kinetics was found for DMA incorporation. The amount of DMA incorporated in the resulting microgel was successfully determined by a combination of UV-vis and NMR spectroscopy to level off limitations of both methods. The dependence of the hydrodynamic radius on temperature was determined by DLS measurements for the microgels. While an early injection of DMA stops the PNIPAM polymerization due to scavenging, it greatly enhances the reaction speed of DMA. The faster reaction of DMA and the incomplete NIPAM and BIS conversion also compensate for shorter reaction times with respect to the incorporated amount of DMA. On the contrary, a later injection of DMA leads to a full NIPAM monomer and BIS cross-linker consumption. An overall reaction time of 60 min ensures the DMA incorporation. Longer reaction times lead to clumping. First adhesion tests show an increased adhesion of P(NIPAM-co-DMA) microgels compared to pure PNIPAM microgels, when mechanical stress is applied.

Effect of Counterions on the Interaction among Concentrated Spherical Polyelectrolyte Brushes.

The effect of counterions on interactions among spherical polyelectrolyte brushes (SPBs) was systematically investigated by rheology, small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The SPB particles consist of a solid polystyrene (PS) core with a diameter of ca.100 nm and a chemically grafted poly-(acrylic acid) (PAA) brush layer. Metal ions of different valences (Na+, Mg2+ and Al3+) were used as counterions to study the interactions among concentrated SPBs. The so-called "structure factor peak" in SAXS, the "local ordered structure peak" in WAXS and rheological properties indicated the interactions among concentrated SPBs. Combining SAXS, WAXS and rheology, the formation mechanism of the local ordered structure among PAA chains in the overlapped area of adjacent SPB, which was generated due to the bridge function of counterions, was confirmed. In contrast, excessive counterions shielded the electrostatic interaction among PAA chains and destroyed the local ordered structure. This work enriches our understanding of the polyelectrolyte assembly in concentrated SPBs under the effect of counterions and lays the foundations for SPB applications.

Coacervation of Spherical Polyelectrolyte Brushes with Additional Polyelectrolytes Bearing Positive or Negative Charges.

By combining small-angle X-ray scattering, wide-angle X-ray scattering, and rheology, the effect of additional polyelectrolyte chains on interactions among spherical polyelectrolyte brushes (SPB) was systematically investigated both on microscopic and macroscopic levels. The negatively charged poly(acrylic acid) (PAA) chains and positively charged poly(dimethyl diallyl ammonium chloride) (PDDA) chains were used as additional polyelectrolyte chains to investigate the local ordered structure and the "polyelectrolyte peak" among SPB. Interestingly, coacervation appeared in the SPB emulsion while introducing additional free polyelectrolyte chains. The addition of excess positively charged PDDA chains would lead to the transformation of the SPB emulsion from the coacervation to the aggregation, while it has not been observed in the case of PAA chains. Moreover, it was further confirmed that the specific local ordered structure was caused by the electrostatic interaction among polyelectrolyte chains of adjacent SPB. This work could enrich our understanding of polyelectrolyte assembly in concentrated SPB, thereby greatly broadening the application fields of SPB.

Spherical Polyelectrolyte Brushes as Templates to Prepare Hollow Silica Spheres Encapsulating Metal Nanoparticles.

Integrating hollow silica spheres with metal nanoparticles to fabricate multifunctional hybrid materials has attracted increasing attention in catalysis, detection, and drug delivery. Here, we report a simple and general method to prepare hollow silica spheres encapsulating silver nanoparticles (Ag@SiO2) based on spherical polyelectrolyte brushes (SPB), which consist of a polystyrene core and densely grafted poly (acrylic acid) (PAA) chains. SPB were firstly used as nanoreactors to generate silver nanoparticles in situ and then used as sacrificial templates to prepare hybrid hollow silica spheres. The resulted Ag@SiO2 composites exhibit high catalytic activity and good reusability for the reduction of 4-nitrophenol to 4-aminophenol by NaBH4. More importantly, this developed approach can be extended to the encapsulation of other metal nanoparticles such as gold nanoparticles into the hollow silica spheres. This work demonstrates that SPB are promising candidates for the preparation of hollow spheres with encapsulated metal nanoparticles and the resulted hybrid spheres show great potential applications in catalysis.

Interaction among Spherical Polyelectrolyte Brushes in Concentrated Aqueous Solution.

Interaction among concentrated spherical polyelectrolyte brushes (SPB) dispersions in water was systematically investigated by means of small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and rheological methods. SPB consist of a core of polystyrene (PS) and a poly(acrylic acid) (PAA) brush shell. The "polyelectrolyte peak" appeared in SAXS spectra and was observed in WAXS curves for the first time. The size of the polyelectrolyte peak and the rheological properties of SPB were found to be strongly effected by SPB concentration, pH, and ionic strength. Combined with SAXS, WAXS, and rheological results, it is confirmed that the polyelectrolyte peak is originated from local ordered structures of polyelectrolyte chains bridged by counterions in the overlapping area among SPB driven by electrostatic interactions.

Facile Fluorescence "Turn on" Sensing of Lead Ions in Water via Carbon Nanodots Immobilized in Spherical Polyelectrolyte Brushes.

Heavy metal detection has become very important for the protection of water resource. In this work, a novel controllable probe is presented for the sensitive detection of Pb2+ in aqueous solutions. The probe was synthesized via the immobilization of surface functionalized carbon dots (named as CAEA-Hs) into the shell of the spherical polyelectrolyte brushes (SPB). The fluorescence of CAEA-H was firstly "turned off" via electrostatic interaction induced quenching. Based on the aggregation induced emission enhancement (AIEE), the fluorescence of the immobilized CAEA-H could be specifically turned on via the aggregation of the SPB particles. This fluorescence "turn on" sensor could selectively detect Pb2+ among five different metal ions with a relatively wide detecting range (0-1.67 mM) and good linear relationship (R 2 = 0.9958). Moreover, the aggregating behavior and nano-structure of CAEA-H loaded SPB have been systematically analyzed via small angle X-ray scattering, turbidity titration, and Zeta-potential measurement. Based on a series of control experiments, we finally gain an insight into the sensing mechanism of this novel sensing probe. This contributed a proof of concept demonstration that sensitive and selective chemical detection can be achieved via a C-dot/SPB synergistic platform.

Preparation and characterization of Ag-Pd bimetallic nano-catalysts in thermosensitive microgel nano-reactor.

Thermosensitive microgels consisting of a solid core of polystyrene and a shell of cross-linked poly(N-isopropylacrylamide) (PNIPA) were synthesized as nano-reactors, in which Ag-Pd bimetallic nanoparticles were prepared through simultaneous in situ reduction reaction. The spatial distribution of metallic nanoparticles in the microgels was analyzed by small angle X-ray scattering (SAXS) and the results indicated that metal nanoparticles were mainly located in the inner layer of microgels. The catalytic activity of Ag-Pd bimetallic nanoparticles was investigated using the reduction of p-nitrophenol to p-aminophenol by NaBH4 as model reaction. The data demonstrated that Ag-Pd bimetallic nanoparticles showed enhanced catalytic activity compared to each monometallic nanoparticle alone and their catalytic activity was controllable by temperature due to the volume transition of PNIPA microgels.

Modification of Spherical Polyelectrolyte Brushes by Layer-by-Layer Self-Assembly as Observed by Small Angle X-ray Scattering.

Multilayer modified spherical polyelectrolyte brushes were prepared through alternate deposition of positively charged poly(allylamine hydrochloride) (PAH) and negatively charged poly-l-aspartic acid (PAsp) onto negatively charged spherical poly(acrylic acid) (PAA) brushes (SPBs) on a poly(styrene) core. The charge reversal determined by the zeta potential indicated the success of layer-by-layer (LBL) deposition. The change of the structure during the construction of multilayer modified SPBs was observed by small-angle X-ray scattering (SAXS). SAXS results indicated that some PAH chains were able to penetrate into the PAA brush for the PAA-PAH double-layer modified SPBs whereas part of the PAH moved towards the outer layer when the PAsp layer was loaded to form a PAA-PAH-PAsp triple-layer system. The multilayer modified SPBs were stable upon changing the pH (5 to 9) and ionic strength (1 to 100 mM). The triple-layer modified SPBs were more tolerated to high pH (even at 11) compared to the double-layer ones. SAXS is proved to be a powerful tool for studying the inner structure of multilayer modified SPBs, which can establish guidelines for the a range of potential applications of multilayer modified SPBs.