This investigation focused on the self-assembly of poly(N-isopropylacrylamide)-block-poly-(ethylene glycol) (PNIPA-block-PEG) in water. A quasi-living radical polymerization technique including a Ce(IV) ion redox system enabled us to prepare block copolymers with relatively narrow molecular weight distributions. We distinguish five regions in the phase diagram: a transparent sol, opaque sol, transparent gel, opaque gel, and syneresis. By examining the extent of changes in the spectroscopic properties of a fluorescence probe, pyrene, as a function of block polymer concentration and/or temperature, we determined the critical association concentration as well as the partition coefficient K v for pyrene. The spectroscopic properties indicate that the hydrophobicity around the probe starts to increase far below the demixing line of the PNIPA-block-PEG, a remarkable finding which suggests that even in the temperature region below the LCST temperature of a PNIPA block (∼32 °C), this block copolymer provides more space for a preferential transfer of pyrene molecules than a bulk water medium at a higher temperature. This result may be attributed to the action of water, which starts to behave as a selective solvent for PEG blocks; the PEG chains are more swollen with water than are the PNIPA chains. Dynamic light scattering measurements also indicate that contraction of the PNIPA block starts to occur around 18 °C, which is consistent with results obtained by fluorescence measurements. By employing small-angle neutron scattering, it is also confirmed that microphase separation occurs above 17 °C to form disordered micelles, which includes a range of states from (i) asymmetric swelling to (ii) micelle formation with only shortrange liquidlike order. Above 30 °C, network domains are formed as a result of macrophase separation due to dehydration of PNIPA blocks. As the temperature increased up to 40 °C, the network domain is collapsed along a direction parallel to PNIPA-block-PEG interface, leading to increase in interfacial thickness and to macroscopic syneresis.
On the basis of results from a small-angle neutron scattering (SANS) study of aqueous solutions of a telechelic PNIPAM with octadecyl end groups, we developed a theoretical model of the self-assembly of this polymer in water as a function of temperature and concentration. This model leads us to the following description. In solutions of concentration 10 g L−1 kept between 10 and 20 °C, telechelic PNIPAMs (M n = 22 200 g mol −1) associate in the form of flower micelles, containing about 12 polymer chains, assembled in a three-layered core−shell morphology with an inner core consisting of the octadecyl units, a dense inner shell consisting of partly collapsed PNIPAM chains, and an outer shell of swollen hydrated chains. Drastic changes in the scattering profile of the solution heated above 31 °C are attributed to the formation of mesoglobules (diameter of ∼40 nm) consisting of about 1000 polymer chains. On further heating, the aggregation number of the mesoglobules increases. It reaches a value of ∼9000 at 34 °C and stays constant upon further heating. In solutions of lower concentration (1 g L−1), association of flower micelles and mesoglobules does not occur; however, the structure of individual flower micelles and mesoglobules is not affected by the change in concentration. In solutions of 50 g L−1 in which flower micelles are expected to be partially connected by bridge chains, a peak attributed to correlation between flower micelles appears in the scattering profiles recorded at low temperature (10−20 °C). In spite of the intermicellar bridging connection, the overall temperature dependence of the scattering profile at 50 g L−1 remains similar to that at 10 g L−1. Distinct features of the self-assembled structures formed in aqueous telechelic PNIPAM solutions are discussed in terms of the interactions between water and the polymer main chains.
Macroscopically anisotropic hydrogels were synthesized by hybridization of poly(N-isopropylacrylamide) with liquid crystalline inorganic nanosheets; their anisotropies in the structure and properties are demonstrated.
Short- and long-range correlations between solutes in solvents can influence the macroscopic chemistry and physical properties of solutions in ways that are not fully understood. The class of liquids known as complex (structured) fluids—containing multiscale aggregates resulting from weak self-assembly—are especially important in energy-relevant systems employed for a variety of chemical- and biological-based purification, separation, and catalytic processes. In these, solute (mass) transfer across liquid–liquid (water, oil) phase boundaries is the core function. Oftentimes the operational success of phase transfer chemistry is dependent upon the bulk fluid structures for which a common functional motif and an archetype aggregate is the micelle. In particular, there is an emerging consensus that mass transfer and bulk organic phase behaviors—notably the critical phenomenon of phase splitting—are impacted by the effects of micellar-like aggregates in water-in-oil microemulsions. In this study, we elucidate the microscopic structures and mesoscopic architectures of metal-, water-, and acid-loaded organic phases using a combination of X-ray and neutron experimentation as well as density functional theory and molecular dynamics simulations. The key conclusion is that the transfer of metal ions between an aqueous phase and an organic one involves the formation of small mononuclear clusters typical of metal–ligand coordination chemistry, at one extreme, in the organic phase, and their aggregation to multinuclear primary clusters that self-assemble to form even larger superclusters typical of supramolecular chemistry, at the other. Our metrical results add an orthogonal perspective to the energetics-based view of phase splitting in chemical separations known as the micellar model—founded upon the interpretation of small-angle neutron scattering data—with respect to a more general phase-space (gas–liquid) model of soft matter self-assembly and particle growth. The structure hierarchy observed in the aggregation of our quinary (zirconium nitrate–nitric acid–water–tri-n-butyl phosphate–n-octane) system is relevant to understanding solution phase transitions, in general, and the function of engineered fluids with metalloamphiphiles, in particular, for mass transfer applications, such as demixing in separation and synthesis in catalysis science.
SANS‐J (a pinhole small‐angle neutron scattering spectrometer at research reactor JRR3, Tokai, Japan) was reconstructed as a focusing and polarized neutron small‐angle scattering spectrometer (SANS‐J‐II). By employing focusing lenses of a biconcave MgF2 crystal or of a sextupole permanent magnet and a high‐resolution photomultiplier, the minimum accessible magnitude of the scattering vector qmin was improved from 3 × 10−3Å−1 to an ultra‐small‐angle scattering (USAS) of 3 × 10−4 Å−1. Compared with a Bonse–Hart double‐crystal method, the advantages of focusing USAS are the efficient detection of anisotropic USAS with an area detector, an improvement in q resolution Δq/q at conventional magnitudes of the scattering vector q ~ 10−3 Å−1 and a gain in neutron flux in the conventional q region of q ~ 10−3 Å−1.
We present evidence that the transition between organic and third phases, which can be observed in the plutonium uranium reduction extraction (PUREX) process at high metal loading, is an unusual transition between two isotropic bicontinuous microemulsion phases. As this system contains so many components, however, we have been seeking first to investigate the properties of a simpler system, namely, the related metal-free, quaternary water/n-dodecane/nitric acid/tributyl phosphate (TBP) system. This quaternary system has been shown to exhibit, under appropriate conditions, three coexisting phases: a light organic phase, an aqueous phase, and the so-called third phase. In the current work, we focused on the coexistence of the light organic phase with the third phase. Using Gibbs ensemble Monte Carlo (GEMC) simulations, we found coexistence of a phase rich in nitric acid and dilute in n-dodecane (the third phase) with a phase more dilute in nitric acid but rich in n-dodecane (the light organic phase). The compositions and densities of these two coexisting phases determined using the simulations were in good agreement with those determined experimentally. Because such systems are generally dense and the molecules involved are not simple, the particle exchange rate in their GEMC simulations can be rather low. To test whether a system having a composition between those of the observed third and organic phases is indeed unstable with respect to phase separation, we used the Bennett acceptance ratio method to calculate the Gibbs energies of the homogeneous phase and the weighted average of the two coexisting phases, where the compositions of these phases were taken both from experimental results and from the results of the GEMC simulations. Both demixed states were determined to have statistically significant lower Gibbs energies than the uniform, mixed phase, providing confirmation that the GEMC simulations correctly predicted the phase separation. Snapshots from the simulations and a cluster analysis of the organic and third phases revealed structures akin to bicontinuous microemulsion phases, with the polar species residing within a mesh and with the surface of the mesh formed by amphiphilic TBP molecules. The nonpolar n-dodecane molecules were observed in these snapshots to be outside this mesh. The only large-scale structural differences observed between the two phases were the dimensions of the mesh. Evidence for the correctness of these structures was provided by the results of small-angle X-ray scattering (SAXS) studies, where the profiles obtained for both the organic and third phases agreed well with those calculated from simulations. Finally, we looked at the microscopic structures of the two phases. In the organic phase, the basic motif was observed to be one nitric acid molecule hydrogen-bonded to a TBP molecule. In the third phase, the most common structure was that of the hydrogen-bonded TBP-HNO-HNO chain. A cluster analysis provided evidence for TBP forming an extended, connected network in both phases. S...
Peptide amphiphile molecules (PA) are remarkably versatile and useful as building blocks for construction of complex supramolecular structures in a bottom-up fashion. Worm-like micelles of PA have been demonstrated to have successful application to creation of synthetic extracellular matrix materials for tissue engineering and regenerative medicine. However, the pathway of the self-assembly process of the PA worm-like micelle has not been fully characterized or understood. This work analyzes the self-assembly process leading to worm-like micelle formation in our designed PA with small-angle neutron scattering and atomic force microscopy. The experimental results demonstrate the existence of transient spherical micelles in the early stage of the process and subsequent micelle chain elongation by attachment of spherical micelles to the end of growing cylindrical micelles to form worm-like micelles in a process mimicking chain-growth polymerization.
In situ and time-resolved small-angle neutron scattering (SANS) was employed for the elucidation of star polymer formation mechanism via linking reaction of living linear polymers in ruthenium-catalyzed living radical polymerization. Here, methyl methacrylate (MMA) was first polymerized with R-Cl/RuCl 2 (PPh 3 ) 3 /tribuylamine (n-Bu 3 N) initiating system, followed by the addition of ethylene glycol dimethacrylate (EGDMA: 3) as a linking agent. After the in situ addition of a small amount of 3 to living linear PMMA, the SANS analysis revealed the following three steps: (process II-1) formation of block copolymers (4) and competitive formation of the small star polymers via the linking reaction of 4 and 4; (process II-2) star-star linking of the small star polymers into star polymers and putting 4 into the core of the star polymers, leading to formation of the microgel-core star polymers; (process II-3) growth of the microgelcore star polymers (5) via placement of 4 into the microgel-core star polymers. Furthermore, the SANS profiles, obtained as a function of polymerization time, were quantitatively analyzed with a core-shell spherical model in order to determine the microstructures of the star polymers: The final reaction product had an average radius of microgel-core (∼1 nm), and average arm numbers N ∼ 17.
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