Thermoresponsive Polymers under Pressure with a Focus on Poly(N-isopropylacrylamide) (PNIPAM).

Pressure is a key variable in the phase behavior of responsive polymers, both for applications and from a fundamental point of view. In this feature article, we review recent developments, particularly applications of neutron techniques such as small-angle neutron scattering (SANS) and quasi-elastic neutron scattering (QENS), across the temperature-pressure phase diagram. These are complemented by kinetic SANS experiments following pressure jumps. In the prototype system poly(N-isopropylacrylamide) (PNIPAM), QENS revealed the pressure-dependent characteristics of hydration water around the lower critical solution temperature transition. The size, water content, and inner structure of the mesoglobules formed in the two-phase region depend strongly on pressure, as shown by SANS. Beside these changes at the phase transition, the mesoglobule formation at low pressure is determined by kinetic factors, namely the formation of a polymer-rich, rigid shell, which hampers further growth by coalescence. At high pressure, in contrast, the growth proceeds by diffusion-limited coalescence without any kinetic hindrance. The disintegration of the mesoglobules evolves either via chain release from their surface or via swelling, depending on the osmotic pressure of the water. Moreover, we report on the profound influence of pressure on the cononsolvency effect. In the temperature-pressure frame, the one-phase region is hugely expanded upon the addition of the cosolvent methanol. SANS experiments unveil the enthalpic and entropic contributions to the effective Flory-Huggins interaction parameter between the segments and the solvent mixture. QENS experiments demonstrate an increase in polymer associated water with pressure, whereas methanol is released. Correspondingly, the solvent phase becomes enriched in methanol, providing a mechanism for the breakdown of cononsolvency at a high pressure. Finally, we outline future opportunities for high-pressure studies of thermoresponsive polymers, with a focus on neutron methods.

Nanoscale disintegration kinetics of mesoglobules in aqueous poly(N-isopropylacrylamide) solutions revealed by small-angle neutron scattering and pressure jumps.

Identification and control of the disintegration mechanism of polymer nanoparticles are essential for applications in transport and release including polymer delivery systems. Structural changes during the disintegration of poly(N-isopropylacrylamide) (PNIPAM) mesoglobules in aqueous solution are studied in situ and in real time using kinetic small-angle neutron scattering with a time resolution of 50 ms. Simultaneously length scales between 1 and 100 nm are resolved. By initiating phase separation through fast pressure jumps across the coexistence line, 3 wt% PNIPAM solutions are rapidly brought into the one-phase state. Starting at the same temperature (35.1 °C) and pressure (17 MPa) the target pressure is varied over the range 25-48 MPa, allowing to systematically alter the osmotic pressure of the solvent within the mesoglobules. Initially, the mesoglobules have a radius of gyration of about 80 nm and contain a small amount of water. Two disintegration mechanisms are identified: (i) for target pressures close to the coexistence line, single polymers are released from the surface of the mesoglobules, and the mesoglobules decrease in size, which takes ∼30 s. (ii) For target pressures more distant from the coexistence line, the mesoglobules are swollen by water, and subsequently the chains become more and more loosely associated. In this case, disintegration proceeds within less than 10 s, controlled by the osmotic pressure of the solvent.

Formation and Growth of Mesoglobules in Aqueous Poly(N-isopropylacrylamide) Solutions Revealed with Kinetic Small-Angle Neutron Scattering and Fast Pressure Jumps.

The phase transition from swollen chains to polymer mesoglobules of an aqueous solution of poly(N-isopropylacrylamide) is investigated with kinetic small-angle neutron scattering with 50 ms time resolution in conjunction with millisecond pressure jumps across the coexistence line. The time-resolved study evidenced three distinct regimes: fractal clusters form during the first second and transform into compact mesoglobules. During the following ∼20 s, these grow by diffusion-limited coalescence. The final step consists of a slow growth characterized by an energy barrier of several kBT. The method opens opportunities for kinetic structural studies of multicomponent systems over wide length and time scales and gives a structural picture spanning from the chain collapse to mesoscopic phase separation.

The Role of Backbone Hydration of Poly(N-isopropyl acrylamide) Across the Volume Phase Transition Compared to its Monomer.

Thermo-responsive polymers undergo a reversible coil-to-globule transition in water after which the chains collapse and aggregate into bigger globules when passing to above its lower critical solution temperature (LCST). The hydrogen bonding with the amide groups in the side chains has to be contrasted with the hydration interaction of the hydrophobic main-chain hydrocarbons. In the present investigation we study molecular changes in the polymer poly(N-isopropyl acrylamide) (PNIPAM) and in its monomer N-isopropyl acrylamide (NIPAM) in solution across the LCST transition. Employing Fourier-transform infrared spectroscopy we probe changes in conformation and hydrogen bonding. We observe a nearly discontinuous shift of the peak frequencies and areas of vibrational bands across the LCST transition for PNIPAM whereas NIPAM exhibits a continuous linear change with temperature. This supports the crucial role of the polymer backbone with respect to hydration changes in the amide group in combination with cooperative interactions of bound water along the backbone chain.

Pressure-Dependence of Poly(N-isopropylacrylamide) Mesoglobule Formation in Aqueous Solution.

Above their cloud point, aqueous solutions of the thermoresponsive polymer poly(N-isopropylacrylamide) (PNIPAM) form large mesoglobules. We have carried out very small-angle neutron scattering (VSANS with q = 0.21-2.3 × 10-3 Å-1) and Raman spectroscopy experiments on a 3 wt % PNIPAM solution in D2O at atmospheric and elevated pressures (up to 113 MPa). Raman spectroscopy reveals that, at high pressure, the polymer is less dehydrated upon crossing the cloud point. VSANS shows that the mesoglobules are significantly larger and contain more D2O than at atmospheric pressure. We conclude that the size of the mesoglobules and thus their growth process are closely related to the hydration state of PNIPAM.

The sole tryptophan of amicyanin enhances its thermal stability but does not influence the electronic properties of the type 1 copper site.

The cupredoxin amicyanin possesses a single tryptophan residue, Trp45. Its fluorescence is quenched when copper is bound even though it is separated by 10.1Å. Mutation of Trp45 to Ala, Phe, Leu and Lys resulted in undetectable protein expression. A W45Y amicyanin variant was isolated. The W45Y mutation did not alter the spectroscopic properties or intrinsic redox potential of amicyanin, but increased the pKa value for the pH-dependent redox potential by 0.5 units. This is due to a hydrogen-bond involving the His95 copper ligand which is present in reduced W45Y amicyanin but not in native amicyanin. The W45Y mutation significantly decreased the thermal stability of amicyanin, as determined by changes in the visible absorbance of oxidized amicyanin and in the circular dichroism spectra for oxidized, reduced and apo forms of amicyanin. Comparison of the crystal structures suggests that the decreased stability of W45Y amicyanin may be attributed to the loss of a strong interior hydrogen bond between Trp45 and Tyr90 in native amicyanin which links two of the ß-sheets that comprise the overall structure of amicyanin. Thus, Trp45 is critical for stabilizing the structure of amicyanin but it does not influence the electronic properties of the copper which quenches its fluorescence.

Luminescence properties of europium-doped cerium oxide nanoparticles: role of vacancy and oxidation states.

Enhancing the optical emission of cerium oxide nanoparticles is essential for potential biomedical applications. In the present work, we report a simple chemical precipitation technique to synthesize europium-doped cerium oxide nanostructures to enhance the emission properties. Structural and optical properties showed an acute dependence on the concentration of oxygen ion vacancy and trivalent cerium, which, in turn, could be modified by dopant concentration and the annealing temperature. Results from X-ray photoelectron spectroscopy showed an increase in tetravalent cerium concentration to 85% on annealing at 900 degrees C. The concentration of oxygen ion vacancy increased from 1.7x10(20) cm(-3) to 4.1x10(20) cm(-3) with the increase in dopant concentration. Maximum emission at room temperature was obtained for 15 mol % Eu-doped ceria, which improved with annealing temperature. The role of oxygen ion vacancies and trivalent cerium in modifying the emission properties is discussed.

Dopant-mediated oxygen vacancy tuning in ceria nanoparticles.

Ceria nanoparticles with 20 and 40 at.% RE (RE = Y, Sm, Gd, and Yb) dopants were synthesized through a microemulsion method. Independently of the dopant nature and concentration, nearly monodispersed nanoparticles of size 3-5 nm were observed in high resolution transmission electron microscopic analysis. The ceria lattice either expands or contracts depending on the dopant cation ionic radii, as indicated by x-ray diffraction studies. X-ray photoelectron and Raman spectroscopic studies were used to quantify the cerium oxidation state and oxygen vacancy concentration. The results show the tunability of the oxygen vacancy and Ce(3+) concentrations based on the dopant properties. First principles simulations using the free energy density functional theory method support the observed experimental trends. The reported results establish a relationship between the oxygen vacancies and oxidation states in doped ceria required for tailoring properties in catalytic and biomedical applications.

Raman gain measurements of thallium-tellurium oxide glasses.

Several different compositions of tellurium-thallium oxide glasses were fabricated and tested for their Raman gain performance. The addition of PbO to the glass matrix increased the surface optical damage threshold by 60-230%. The maximum material Raman gain coefficient experimentally obtained was (58 +/- 3) times higher than the peak Raman gain of a 3.18 mm thick Corning 7980-2F fused silica sample (Deltanu = 13.2 THz). The highest peak in the Raman gain spectrum of the tellurium-thallium glass is attributed to the presence of TeO3 and TeO3+1 structural units with thallium ions in the vicinity at a frequency shift near 21.3 THz.

Direct femtosecond laser writing of waveguides in As2S3 thin films.

Single-channel waveguides and Y couplers were fabricated in chalcogenide thin films by use of femtosecond laser pulses from a 25-MHz repetition rate Ti:sapphire laser. Refractive-index differentials (delta n > 10(-2)) were measured through interferometric microscopy and are higher than the typical values reported for oxide glasses. The dependence of the index differential on the peak intensity reveals the nonlinear nature of the photosensitivity in arsenic trisulfide below its bandgap energy, and the refractive-index change is correlated to the photoinduced structural changes inferred by Raman spectroscopy data. A free-electron model to predict the parametric dependence of delta n is proposed.

Direct estimation of biofilm density on different pipe material coupons using a specific DNA-probe.

A variety of approaches to quantify biomass in biofilms without disruption due to detachment have been developed over the years. One basic approach is the combination of advanced microscopy with molecular staining. However, many stains (e.g. 4',6-diamino-2-phenylindole, acridine orange or live-dead stains) can be non-specific when corrosion products, precipitates, and pipe material are present. In addition, some pipe materials cause high background when using epifluorescent microscopy. The new refinement discussed in this presentation used fluorescence spectroscopy to obtain the spectra from four common distribution system pipe materials: PVC, 'concrete' lined cast iron, cast iron, and galvanized steel. The emission maximum for all four materials was between 500 and 550 nm, but emissions radically decreased around 575-600 nm. A molecular probe, BO-PRO-3 (Molecular Probes, Inc., Eugene, OR, USA) was identified which has an emission intensity maximum at 599 nm (red), with emission intensity 200 times greater when it is bound to DNA. The BO-PRO-3 has greatly reduced non-specific staining and background problems. In the preliminary experiment, using diluted waste water, a significant exponential relationship was found between stained surface area/total area ratio and fixed biofilm inventory measurements from scraping heterotrophic plate counts (SHPC) on R2A medium. In addition, the biofilm inventory on different pipe material coupons from pilot distribution systems was also correlated to the stained surface area fraction and SHPC.

Tellurite glasses with peak absolute Raman gain coefficients up to 30 times that of fused silica.

An experimental system has been assembled to measure the absolute values of the Raman gain spectrum for millimeter-thick glass samples. Results are reported for two new oxide glasses with Raman gain coefficients as much as 30 times larger than that of fused silica and more than twice its spectral coverage.