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A comprehensive molecular analysis of a simple aqueous complexing system. U(VI) acetate. selected to be independently investigated by various spectroscopic (vibrational, luminescence, X-ray absorption, and nuclear magnetic resonance spectroscopy) and quantum chemical methods was achieved by an international round-robin test (RRT). Twenty laboratories from six different countries with a focus on actinide or geochemical research participated and contributed to this scientific endeavor. The outcomes of this RRT were considered on two levels of complexity: first, within each technical discipline, conformities as well as discrepancies of the results and their sources were evaluated. The raw data from the different experimental approaches were found to be generally consistent. In particular, for complex setups such as accelerator-based X-ray absorption spectroscopy, the agreement between the raw data was high. By contrast, luminescence spectroscopic data turned out to be strongly related to the chosen acquisition parameters. Second, the potentials and limitations of coupling various spectroscopic and theoretical approaches for the comprehensive study of actinide molecular complexes were assessed. Previous spectroscopic data from the literature were revised and the benchmark data on the U(VI) acetate system provided an unambiguous molecular interpretation based on the correlation of spectroscopic and theoretical results. The multimethodologic approach and the conclusions drawn address not only important aspects of actinide spectroscopy but particularly general aspects of modern molecular analytical chemistry.
Birth weight variation is influenced by fetal and maternal genetic and non-genetic factors, and has been reproducibly associated with future cardio-metabolic health outcomes. In expanded genome-wide association analyses of own birth weight (n = 321,223) and offspring birth weight (n = 230,069 mothers), we identified 190 independent association signals (129 of which are novel). We used structural equation modeling to decompose the contributions of direct fetal and indirect maternal genetic effects, then applied Mendelian randomization to illuminate causal pathways. For example, both indirect maternal and direct fetal genetic effects drive the observational relationship between lower birth weight and higher later blood pressure: maternal blood pressure-raising alleles reduce offspring birth weight, but only direct fetal effects of these alleles, once inherited, increase later offspring blood pressure. Using maternal birth weight-lowering genotypes to proxy for an adverse intrauterine environment provided no evidence that it causally raises offspring blood pressure, indicating that the inverse birth weight-blood pressure association is attributable to genetic effects, and not to intrauterine programming.
Swelling and switching kinetics of gold coated end-capped poly(N-isopropylacrylamide) thin films
(2010)
Thin thermoresponsive hydrogel films of poly(N-isopropylacrylamide) end-capped with n-butyltrithiocarbonate(nbc- PNIPAM) oil si I icon supports with a gold layer on top, causing an asymmetric confinement, are investigated. For two different gold layer thicknesses (nominally 0.4 and 5 rim), the swelling and switching kinetics are probed with in situ neutron reflectivity. With a temperature jump from 23 to 40 degrees C the film is switched from a swollen into a collapsed state. For the thin gold layer this switching is faster as compared to the thick gold layer. The switching is a two-step process of water release and a subsequent structural relaxation. fit swelling and deswelling cycles, aging of the films is probed. After five cycles, the film exhibits enhanced water storage capacity. Grazing-incidence small-angle X-ray scattering (GISAXS) shows that these gold coated nbc-PNIPAM films do not age with respect to the inner structure but slightly roughen at the gold surface. As revealed by atomic force microscopy, the morphology of the gold layer is changed by the water uptake and release.
The free volume in thin films of poly(N-isopropylacrylamid) end-capped with n-butyltrio-carbonate (nbc-PNIPAM) is probed with positron annihilation lifetime spectroscopy (PALS). The PALS measurements are performed as function of energy to obtain depth profiles of the free volume of nbc-PNIPAM films. The range of nbc-PNIPAM films with thicknesses from 40 to 200 nm is focused. With decreasing film thickness the free volume increases in good agreement with an increase in the maximum swelling capability of the nbc-PNIPAM films. Thus in thin hydrogel films the sorption and swelling behavior is governed by free volume.
Reliability tests for wavelength-stabilized compact diode laser systems emitting at 671 nm are presented. The devices were mounted on microoptical benches with the dimensions of 13 mm x 4 mm. Reflecting Bragg gratings were used for wavelength stabilization and emission width narrowing. The reliability tests were performed at 25 degrees C and at an output power up to 10 mW per micrometer stripe width of the gain medium. Reliable operation could be demonstrated over a test time up to 14 500 h at an output power up to 1.0 W. Environmental tests using random vibrations with acceleration up to 29 g were performed without deterioration of the devices.
The swelling and co-nonsolvency behaviors in pure H2O and in a mixed H2O/CH3OH vapor atmosphere of two different polar, water-soluble polymers in thin film geometry are studied in situ. Films of a zwitterionic poly(sulfobetaine), namely, poly[3-((2-(methacryloyloxy)ethyl)dimethylammonio) propane-1-sulfonate] (PSPE), and a polar nonionic polymer, namely, poly(N-isopropylmethacrylamide) (PNIPMAM), are investigated in real time by spectral reflectance (SR) measurements and Fourier transform infrared (FTIR) spectroscopy. Whereas PSPE is insoluble in methanol, PNIPMAM is soluble but exhibits cononsolvency behavior in water/methanol mixtures. First, the swelling of PSPE and PNIPMAM thin films in H2O vapor is followed. Subsequently, CH3OH is added to the vapor atmosphere, and its contracting effect on the water-swollen films is monitored, revealing a co-nonsolvency-type behavior for PNIPMAM and PSPE. SR measurements indicate that PSPE and PNIPMAM behave significantly different during the H2O swelling and subsequent exposure to CH3OH, not only with respect to the amounts of absorbed water and CH3OH, but also to the cosolvent-induced contraction mechanisms. While PSPE thin films exhibit an abrupt one-step contraction, the contraction of PNIPMAM thin films occurs in two steps. FTIR studies corroborate these findings on a molecular scale and reveal the role of the specific functional groups, both during the swelling and the cosolvent-induced switching of the solvation state.
The water vapor-induced swelling, as well as subsequent phase-transition kinetics, of thin films of a diblock copolymer (DBC) loaded with different amounts of the salt NaBr, is investigated in situ. In dilute aqueous solution, the DBC features an orthogonally thermoresponsive behavior. It consists of a zwitterionic poly(sulfobetaine) block, namely, poly(4-(N-(3'-methacrylamidopropyl)-N, N-dimethylammonio) butane-1-sulfonate) (PSBP), showing an upper critical solution temperature, and a nonionic block, namely, poly(N-isopropylmethacrylamide) (PNIPMAM), exhibiting a lower critical solution temperature. The swelling kinetics in D2O vapor at 15 degrees C and the phase transition kinetics upon heating the swollen film to 60 degrees C and cooling back to 15 degrees C are followed with simultaneous time-of-flight neutron reflectometry and spectral reflectance measurements. These are complemented by Fourier transform infrared spectroscopy. The collapse temperature of PNIPMAM and the swelling temperature of PSBP are found at lower temperatures than in aqueous solution, which is attributed to the high polymer concentration in the thin-film geometry. Upon inclusion of sub-stoichiometric amounts (relative to the monomer units) of NaBr in the films, the water incorporation is significantly increased. This increase is mainly attributed to a salting-in effect on the zwitterionic PSBP block. Whereas the addition of NaBr notably shifts the swelling temperature of PSBP to lower temperatures, the collapse temperature of PNIPMAM remains unaffected by the presence of salt in the films.
The water swelling and subsequent solvent exchange including co-nonsolvency behavior of thin films of a doubly thermo-responsive diblock copolymer (DBC) are studied viaspectral reflectance, time-of-flight neutron reflectometry, and Fourier transform infrared spectroscopy.
The DBC consists of a thermo-responsive zwitterionic (poly(4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate)) (PSBP) block, featuring an upper critical solution temperature transition in aqueous media but being insoluble in acetone, and a nonionic poly(N-isopropylmethacrylamide) (PNIPMAM) block, featuring a lower critical solution temperature transition in water, while being soluble in acetone.
Homogeneous DBC films of 50-100 nm thickness are first swollen in saturated water vapor (H2OorD2O), before they are subjected to a contraction process by exposure to mixed saturated water/acetone vapor (H2OorD2O/acetone-d6 = 9:1 v/v).
The affinity of the DBC film toward H2O is stronger than for D2O, as inferred from the higher film thickness in the swollen state and the higher absorbed water content, thus revealing a pronounced isotope sensitivity.
During the co-solvent-induced switching by mixed water/acetone vapor, a two-step film contraction is observed, which is attributed to the delayed expulsion of water molecules and uptake of acetone molecules.
The swelling kinetics are compared for both mixed vapors (H2O/acetone-d6 and D2O/acetone-d6) and with those of the related homopolymer films.
Moreover, the concomitant variations of the local environment around the hydrophilic groups located in the PSBP and PNIPMAM blocks are followed.
The first contraction step turns out to be dominated by the behavior of the PSBP block, where as the second one is dominated by the PNIPMAM block.
The unusual swelling and contraction behavior of the latter block is attributed to its co-nonsolvency behavior.
Furthermore, we observe cooperative hydration effects in the DBC films, that is, both polymer blocks influence each other's solvation behavior.
Polysulfobetaines in aqueous solution show upper critical solution temperature (UCST) behavior. We investigate here the representative of this class of materials, poly (N,N-dimethyl-N-(3-methacrylamidopropyl) ammonio propane sulfonate) (PSPP), with respect to: (i) the dynamics in aqueous solution above the cloud point as function of NaBr concentration; and (ii) the swelling behavior of thin films in water vapor as function of the initial film thickness. For PSPP solutions with a concentration of 5 wt.%, the temperature dependence of the intensity autocorrelation functions is measured with dynamic light scattering as function of molar mass and NaBr concentration (0-8 mM). We found a scaling of behavior for the scattered intensity and dynamic correlation length. The resulting spinodal temperatures showed a maximum at a certain (small) NaBr concentration, which is similar to the behavior of the cloud points measured previously by turbidimetry. The critical exponent of susceptibility depends on NaBr concentration, with a minimum value where the spinodal temperature is maximum and a trend towards the mean-field value of unity with increasing NaBr concentration. In contrast, the critical exponent of the correlation length does not depend on NaBr concentration and is lower than the value of 0.5 predicted by mean-field theory. For PSPP thin films, the swelling behavior was found to depend on film thickness. A film thickness of about 100 nm turns out to be the optimum thickness needed to obtain fast hydration with H2O.
In aqueous solution, symmetric triblock copolymers with a thermoresponsive middle block and hydrophobic end blocks form flower-like core-shell micelles which collapse and aggregate upon heating through the cloud point (CP). The collapse of the micellar shell and the intermicellar aggregation are followed in situ and in real-time using time-resolved small-angle neutron scattering (SANS), while heating micellar solutions of a poly((styrene-d(8))-b-(N-isopropyl acrylamide)-b-(styrene-d(8))) triblock copolymer in D2O rapidly through their CP. The influence of polymer concentration as well as of the start and target temperatures is addressed. In all cases, the micellar collapse is very fast. The collapsed micelles immediately form small clusters which contain voids. They densify which slows down or even stops their growth. For low concentrations and target temperatures just above the CP, i.e. shallow temperature jumps, the subsequent growth of the clusters is described by diffusion-limited aggregation. In contrast, for higher concentrations and/or higher target temperatures, i.e. deep temperature jumps, intermicellar bridges dominate the growth. Eventually, in all cases, the clusters coagulate which results in macroscopic phase separation. For shallow temperature jumps, the cluster surfaces stay rough; whereas for deep temperature jumps, a concentration gradient develops at late stages. These results are important for the development of conditions for thermal switching in applications, e.g. for the use of thermoresponsive micellar systems for transport and delivery purposes.