Glass and Jamming Rheology in Soft Particles Made of PNIPAM and Polyacrylic Acid

The phase behaviour of soft colloids has attracted great attention due to the large variety of new phenomenologies emerging from their ability to pack at very high volume fractions. Here we report rheological measurements on interpenetrated polymer network microgels composed of poly(N-isopropylacrylamide) (PNIPAM) and polyacrylic acid (PAAc) at fixed PAAc content as a function of weight concentration. We found three different rheological regimes characteristic of three different states: a Newtonian shear-thinning fluid, an attractive glass characterized by a yield stress, and a jamming state. We discuss the possible molecular mechanisms driving the formation of these states.     

Effect of pH,co-monomer content,and surfactant structure on the swelling behavior of microgel-azobenzene-containing surfactant complex

The contraction/swelling transition of anionic PNIPAM-co-AAA particles can be manipulated by light using interactions with cationic azobenzene-containing surfactant. In this study the influence of pH-buffers and their concentrations, the charge density (AAA content) in microgel particles as well as the spacer length of the surfactant on the complex formation between the microgel and surfactant is investigated. It is shown that the presence of pH buffer can lead to complete blocking of the interactions in such complexes and the resulting microgel contraction/swelling response. There is a clear competition between the buffer ions and the surfactant molecules interacting with microgel particles. When working in pure water solutions with fixed concentration (charge density) of microgel, the contraction/swelling of the particles is controlled only by relative concentration (charge ratio) of the surfactant and AAA groups of the microgel. Furthermore, the particle contraction is more efficient for shorter spacer length of the surfactant. The onset point of the contraction process is not affected by the surfactant hydrophobicity. This work provides new insight into the interaction between microgel particles and photo-sensitive surfactants, which offers high potential in new sensor systems.     

Interpolymer radical coupling: A toolbox complementary to controlled radical polymerization

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular engineering toolbox to the controlled radical polymerization techniques (CRP). Indeed, all structures formed by CRP are likely to be prone to radical coupling reactions, which multiply the available synthetic possibilities. Basically, the coupling systems can be divided in two main categories. The first one, including the atom transfer radical coupling (ATRC), silane radical atom abstraction (SRAA) and cobalt-mediated radical coupling (CMRC), relies on the recombination of macroradicals produced from a dormant species. The second one, including atom transfer nitroxide radical coupling (ATNRC), single electron transfer nitroxide radical coupling (SETNRC), enhanced spin capturing polymerization (ESCP) and nitrone/nitroso mediated radical coupling (NMRC), makes use of a radical scavenger in order to promote the conjugation of the polymer chains. More than a compilation of macromolecular engineering achievements, the present review additionally aims to emphasize the particularities, synthetic potential and present limitations of each system.     

Co-nonsolvency effects in the thermoprecipitation of oligomeric polyacrylamides from hydro-organic solutions

Co-solutes and co-solvents influence the thermoprecipitation of stimulus-responsive polymers from aqueous solution. Taking the behavior of oligomeric poly-(N-isopropylacrylamide) prepared by chain transfer polymerization as reference, the influence of organic solvents (concentration <2 M) on the thermoprecipitation of polyacrylamides with critical solution temperatures (CST) in pure water between 30 and 75 °C is investigated using turbidity and differential scanning calorimetry. Depending on the system, both increase and decrease but also the disappearance of the CST is observed. The strength of the observed effect is related not only to the size but also the structure of the hydrophobic domain of the solvent molecule. Contrary to the effects observed upon the addition of simple salts as additives, the chemistry of the investigated polyacrylamide is of direct consequence for the effect of a given solvent. Certain parallels can hence be drawn to the behavior previously observed for additives such as anionic surfactants and alkylamines.     

Swelling and thermal properties of porous PNIPAM/PEG hydrogels prepared by radiation polymerization

In this study,a series of porous intelligent hydrogels were synthesized by radiation exhibiting the lower critical solution temperature（LCST） and fast response involving a combination of A’-isopropyl acrylamideas monomer, polyethylene glycol（PEG） as pore-forming agent and N,N-methylene-bis-acrylamide as crosslinking agent.The hydrogels were analyzed by Fourier transform infrared spectroscopy,and the influence of radiation doses on their swelling and thermal behaviors were studied.Their surface morphologies were examined by scanning electron microscopy.The results showed that PEG molecules only acted as pore-forming agent in the cross-linked polymerization.Their swelling ratios reduced with increasing radiation doses.The LCST was around 37℃,and varied little with the radiation doses.The frozen water content of PNIPAM/PEG₆₀₀₀ hydrogel reduced with increasing the radiation dose,and was greater than that of PN1PAM hydrogel at 15 kGy.Hydrogel macropores were prepared by PEG agent,and the hydrogels without PEG had a dense surface.The porous hydrogels are expected to be applied in the field of artificial intelligence material.     

Synthesis and functionalization of nanoengineered materials using click chemistry

The synthesis of nanoengineered materials with precise control over material composition, architecture and functionality is integral to advances in diverse fields, including biomedicine. Over the last 10 years, click chemistry has emerged as a prominent and versatile approach to engineer materials with specific properties. Herein, we highlight the application of click chemistry for the synthesis of nanoengineered materials, ranging from ultrathin films to delivery systems such as polymersomes, dendrimers and capsules. In addition, we discuss the use of click chemistry for functionalizing such materials, focusing on modifications aimed at biomedical applications.     

Photothermally Sensitive Poly(N‐isopropylacrylamide)/Graphene Oxide Nanocomposite Hydrogels as Remote Light‐Controlled Liquid Microvalves

A photothermally sensitive poly(N‐isopropylacrylamide)/graphene oxide (PNIPAM/GO) nanocomposite hydrogel can be synthesized by in situ γ‐irradiation‐assisted polymerization of an aqueous solution of N‐isopropylacrylamide monomer in the presence of graphene oxide (GO). The colors and phase‐transition temperatures of the PNIPAM/GO hydrogels change with different GO doping levels. Due to the high optical absorbance of the GO, the nanocomposite hydrogel shows excellent photothermal properties, where its phase transitions can be controlled remotely by near‐infrared (NIR) laser irradiation, and it is completely reversible via laser exposure or non‐exposure. With a higher GO loading, the NIR‐induced temperature of the nanocomposite hydrogel increases more quickly than with a lower doping level and the temperature can be tuned effectively by the irradiation time. The nanocomposite hydrogel with its excellent photothermal properties will have great applications in the biomedical field, especially as microfluidic devices; this has been demonstrated in our experiments by way of remote microvalves to control fluidic flow. Such an “easy” and “clean” synthetic procedure initiated by γ‐irradiation can be extended for the efficient synthesis of other nanocomposite materials.