Poly(N-isopropylacrylamide) (PNIPAM) is one of the most well studied thermoresponsive polymers and its microgels undergo a reversible volume phase transition (VPT) at temperatures close to that of the human body. Coupling this property with the unique optical properties of single-walled carbon nanotubes (SWCNT) in the near infrared (NIR) leads to interesting nanohybrids that could be used as multi-responsive sensors/actuators for biological applications.We show the synthesis of thermoresponsive SWCNT/PNIPAM hybrids using two different non-covalent strategies, preserving the nanotube optical properties such as fluorescence. The first strategy involves the dispersion of the SWCNT in water with sodium dodecyl sulfate (SDS), and subsequent in situ synthesis of PNIPAM microgels inside the SDS coatings around the nanotubes. The second strategy starts with modifying the nanotubes with a pyrene derivative, which in turn is used as the starting point for the in situ polymerization of the PNIPAM microgels, thus ensuring that the polymer grows around the nanotubes. In both cases, we obtain hybrids showing a phase transition at temperatures close to that of the human body, with the absorption and fluorescence spectra of the hybrids in the NIR changing in response to the changing dielectric environment. These systems could be used as actuators/sensors in biological systems.

ContextSingle-wall carbon nanotubes (SWCNT) dispersed in water with the help of sodium dodecyl sulfate (SDS) surfactants exhibit a temperature dependent near infrared (NIR) exciton spectrum. Due to their biocompatibility and NIR spectrum falling within the transparent window for biological tissue, SWCNTs hold potential for sensing temperature inside cells. Here, we seek to elucidate the mechanism responsible for this temperature dependence, focusing on changes in the water coverage of the SWCNT as the surfactant structure changes with temperature. We compare optical absorption spectra in the UV–Vis-IR range and fully atomistic molecular dynamics (MD) simulations. The observed temperature dependence of the spectra for various SWCNTs may be attributed to changes in the dielectric environment and its impact on excitons. MD simulations reveal that the adsorbed SDS molecules effectively shield the SWCNT, with ~ 70% of water molecules removed from the first two adlayers; this coverage shows a modest temperature dependence. Although we are not able to directly demonstrate how this influences the NIR spectrum, this represents a potential pathway given the strong influence of the water environment on the excitons in SWCNTs.MethodsOptical absorption measurements were carried out in the UV–Vis-NIR range using a Varian Cary 5000 spectrophotometer in a temperature-controlled environment. PeakFit™ v. 4.06 was used as peak-fitting program in the spectral range 900–1400 nm (890–1380 meV) as a function of the temperature. Fully atomistic molecular dynamics simulations were conducted using the NAMD2 package. The CHARMM force field comprising two-body bond stretching, three-body angle deformation, four-body dihedral angle deformation, and nonbonded interactions (electrostatic and Lennard–Jones 6–16 potentials) was employed.

Mesoporous systems are ubiquitous in membrane science and applications due to their high internal surface area and tunable pore size. A new synthesis pathway of hydrolytic ionosilica films with mesopores formed by ionic liquid (IL) templating is proposed and compared to the traditional non-hydrolytic strategy. For both pathways, the multi-scale formation of pores has been studied as a function of IL content, combining results of thermogravimetric analysis (TGA), nitrogen sorption, and small-angle X-ray scattering (SAXS). The combination of TGA and nitrogen sorption provides access to ionosilica and pore volume fractions, with contributions of meso- and macropores. We then elaborate an original and quantitative geometrical model to analyze the SAXS data based on small spheres (Rs = 1 – 2 nm) and cylinders (Lcyl = 10 – 20 nm) with radial polydispersity provided by the nitrogen sorption isotherms. As a main result, we found that for a given incorporation of templating IL, both synthesis pathways produce very similar pore geometries, but the better incorporation efficacy of the new hydrolytic films provides a higher mesoporosity. Our combined study provides a coherent view of mesopore geometry, and thereby an optimization pathway of porous ionic membranes in terms of accessible mesoporosity contributing to the specific surface. Possible applications include electrolyte membranes of improved ionic properties, e.g., in fuel cells and batteries, as well as molecular storage.

The addition of water to native cellulose/1-ethyl-3methylimidazolium acetate solutions catalyzes the formation of gels, where polymer chain-chain intermolecular associations act as cross-links. However, the relationship between water content (Wc), polymer concentration (Cp), and gel strength is still missing. This study provides the fundamentals to design water-induced gels. First, the sol-gel transition occurs exclusively in entangled solutions, while in unentangled ones, intramolecular associations hamper interchain cross-linking, preventing the gel formation. In entangled systems, the addition of water has a dual impact: at low water concentrations, the gel modulus is water-independent and controlled by entanglements. As water increases, more cross-links per chain than entanglements emerge, causing the modulus of the gel to scale as Gp ∼ C p^2 Wc^3.0±0.2. Immersing the solutions in water yields hydrogels with noncrystalline, aggregate-rich structures. Such water-ionic liquid exchange is examined via Raman, FTIR, and WAXS. Our findings provide avenues for designing biogels with desired rheological properties.

Optical metasurfaces are two-dimensional assemblies of nanoscale optical resonators and could constitute the next-generation of ultra-thin optical components. The development of methods to manufacture those nanostructures on a large scale is still a challenge, while most performance demonstrations were obtained with lithographically fabricated metasurfaces, that are restricted to small scales. Self-assembly fabrication routes are scattering of the nanoresonators in a meta-fluid, and show that they present strong optical magnetic resonances and directional forward scattering patterns, with scattering efficiencies of up to 4. The metasurfaces consist in homogeneous films, of variable surface density, of colloidal clusters which have the same extinction properties on the surface and in the fluid. This experimental approach allows for the large scale production of metasurfaces.

Plastic pollution in the aquatic environment has been assessed for many years by ocean waste collection expeditions around the globe or by river sampling. While the total amount of plastic produced worldwide is well documented, the amount of plastic found in the ocean, the distribution of particles on its surface and its evolution over time are still the subject of much debate. In this article, we propose a general fragmentation model, postulating the existence of a critical size below which particle fragmentation becomes extremely unlikely. In the frame of this model, an abundance peak appears for sizes around 1mm, in agreement with real environmental data. Using, in addition, a realistic exponential waste feed to the ocean, we discuss the relative impact of fragmentation and feed rates, and the temporal evolution of microplastics (MP) distribution. New conclusions on the temporal trend of MP pollution are drawn.

Recent studies of self-assembly in binary systems of bio-surfactants, either of microbial origin or saponins extracted from plants, are reviewed. Saponins in water reported in the first section include aescin, glycyrrhizin, and quillaja saponins, while rhamnolipids are discussed in the second section on microbial surfactants. Studies of surface activities are a natural starting point of the characterization of surfactants, but here we focus mainly on physico-chemical and structural properties of self-assembled bulk structures in solution, often characterized by scattering techniques. When quantitative modelling is performed, self-assembly parameters like aggregation numbers, head group areas, and resulting shapes can be followed as a function of physical-chemical parameters like concentration, composition, temperature, or pH. Morphologies include micelles and their structural evolution with addition of other bio- or synthetic surfactants, co-surfactants, proteins or phospholipids.