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The recent development of polymerization-induced self-assembly (PISA) has facilitated the rational synthesis of a range of diblock copolymer worms, which hitherto could only be prepared via traditional post-polymerization processing in dilute solution. Herein we explore a new synthetic route to aqueous dispersions of cationic disulfide-functionalized worm gels. This is achieved via the PISA synthesis of poly[(glycerol monomethacrylate-stat-glycidyl methacrylate)]-block-poly(2-hydroxypropyl methacrylate) (P(GMA-stat-GlyMA)-PHPMA) block copolymer worms via reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of HPMA. A water-soluble reagent, cystamine, is then reacted with the pendent epoxy groups located within the P(GMA-stat-GlyMA) stabilizer chains to introduce disulfide functionality, while simultaneously conferring cationic character via formation of secondary amine groups. Moreover, systematic variation of the cystamine/epoxy molar ratio enables either chemically cross-linked worm gels or physical (linear) primary amine-functionalized disulfide-based worm gels to be obtained. These new worm gels were characterized using gel permeation chromatography, 1H NMR spectroscopy, transmission electron microscopy, dynamic light scattering, aqueous electrophoresis and rheology. In principle, such hydrogels may offer enhanced mucoadhesive properties.

The seasonal pattern of the carbon isotope content (δ13C) of atmospheric CO2 depends on local and nonlocal land-atmosphere exchange and atmospheric transport. Previous studies suggested that the δ13C of the net land-atmosphere CO2 flux (δsource) varies seasonally as stomatal conductance of plants responds to vapor pressure deficit of air (VPD). We studied the variation of δsource at seven sites across the United States representing forests, grasslands, and an urban center. Using a two-part mixing model, we calculated the seasonal δsource for each site after removing background influence and, when possible, removing δ13C variation of nonlocal sources. Compared to previous analyses, we found a reduced seasonal (March–September) variation in δsource at the forest sites (0.5‰ variation). We did not find a consistent seasonal relationship between VPD and δsource across forest (or other) sites, providing evidence that stomatal response to VPD was not the cause of the global, coherent seasonal pattern in δsource. In contrast to the forest sites, grassland and urban sites had a larger seasonal variation in δsource (5‰) dominated by seasonal transitions in C3/C4 grass productivity and in fossil fuel emissions, respectively. Our findings were sensitive to the location used to account for atmospheric background variation within the mixing model method that determined δsource. Special consideration should be given to background location depending on whether the intent is to understand site level dynamics or regional scale impacts of land-atmosphere exchange. The seasonal amplitude in δ13C of land-atmosphere CO2 exchange (δsource) varied across land cover types and was not driven by seasonal changes in vapor pressure deficit. The largest seasonal amplitudes of δsource were at grassland and urban sites, driven by changes in C3/C4 grass productivity and fossil fuel emissions, respectively. Mixing model approaches may incorrectly calculate δsource when background atmospheric observations are remote and/or prone to anthropogenic influence.

© 2016 John Wiley & Sons Ltd Gross ecosystem productivity (GEP) in tropical forests varies both with the environment and with biotic changes in photosynthetic infrastructure, but our understanding of the relative effects of these factors across timescales is limited. Here, we used a statistical model to partition the variability of seven years of eddy covariance-derived GEP in a central Amazon evergreen forest into two main causes: variation in environmental drivers (solar radiation, diffuse light fraction, and vapor pressure deficit) that interact with model parameters that govern photosynthesis and biotic variation in canopy photosynthetic light-use efficiency associated with changes in the parameters themselves. Our fitted model was able to explain most of the variability in GEP at hourly (R2= 0.77) to interannual (R2= 0.80) timescales. At hourly timescales, we found that 75% of observed GEP variability could be attributed to environmental variability. When aggregating GEP to the longer timescales (daily, monthly, and yearly), however, environmental variation explained progressively less GEP variability: At monthly timescales, it explained only 3%, much less than biotic variation in canopy photosynthetic light-use efficiency, which accounted for 63%. These results challenge modeling approaches that assume GEP is primarily controlled by the environment at both short and long timescales. Our approach distinguishing biotic from environmental variability can help to resolve debates about environmental limitations to tropical forest photosynthesis. For example, we found that biotically regulated canopy photosynthetic light-use efficiency (associated with leaf phenology) increased with sunlight during dry seasons (consistent with light but not water limitation of canopy development) but that realized GEP was nonetheless lower relative to its potential efficiency during dry than wet seasons (consistent with water limitation of photosynthesis in given assemblages of leaves). This work highlights the importance of accounting for differential regulation of GEP at different timescales and of identifying the underlying feedbacks and adaptive mechanisms.

ROSANNE is a collaborative project in the 7th EU Framework Program which aims at harmonizing measurement methods for skid resistance, noise emission and rolling resistance of road pavements as a preparation for standardization. The project started in November 2013 and is developing and improving standards in the field of working group CEN/TC227/WG5. Regarding the influence of the pavement on the road traffic noise emission, the main objective is to combine the existing measurement methods of SPB (ISO 11819-1) and CPX (ISO/DIS 11819-2) into a stable and reliable harmonized pavement noise emission characterization method. A respective procedure is being developed within the project and its potential use for noise calculation methods like the one proposed by the CNOSSOS-EU project is investigated. The first two years of research focused on analysing and comparing existing noise measurement methods to specify the noise properties of road surfaces as well as investigating the temperature influence of possible correction measures; respective results will be presented in a separate paper on this issue within this conference. Activities related to the compatibility with the CNOSSOS-EU calculation method and to the experimental validation are still ongoing. The present paper shows the current draft of the procedure developed.

An intensity-stabilized diode laser absorption spectrometer was developed and used to perform a highly accurate study of the line shape of CO(2) absorption lines, in the spectral region around 5000 cm(-1), belonging to the nu(1) + 2nu(2)(0) + nu(3) combination band, at a temperature of 296.00 K. Standard and complex semiclassical models, including Dicke narrowing and speed-dependent broadening effects, were applied, tested, and compared in the pressure range between 0.7 and 4 kPa, in order to single out the model best reproducing the absorption profile and, hence, the physical situation of self-colliding CO(2) molecules. Line intensity factors and self-broadening coefficients were determined. The 1-sigma overall accuracy of our determinations is at a level of 0.1%, which is, to our knowledge, the highest ever reached.

We report on the design and laboratory performance of a portable infrared absorption spectrometer for the measurement of the isotopic ratio 13C:12C in CO2. The design relies on optical feedback cavity-enhanced absorption spectroscopy in the 2 μm spectral region to achieve optimal performance at ambient CO2 concentrations. The prototype instrument measures δ13C, relative to a standard calibration bottle, with a precision of ±0.7‰ for a 20-s integration time and with an automatic recalibration every 6 min. The absolute accuracy obtained is 0.9‰. The principal performance limitations are discussed along with improvements currently being implemented for the second generation instrument.

We report on a new optical implementation of primary gas thermometry based on laser absorption spectrometry in the near infrared. The method consists in retrieving the Doppler broadening from highly accurate observations of the line shape of the R(12) $\nu_{1} + 2 \nu_{2}^{\phantom{1}0} + \nu_{3}$ transition in CO$_{2}$ gas at thermodynamic equilibrium. Doppler width measurements as a function of gas temperature, ranging between the triple point of water and the gallium melting point, allowed for a spectroscopic determination of the Boltzmann constant with a relative accuracy of $\sim1.6\times10^{-4}$., Comment: Submitted to Physical Review Letters

An intensity-stabilized laser absorption spectrometer, which incorporates a mirror-extended cavity diode laser, a temperature-stabilized gas cell, and a Michelson interferometer, was developed and applied to a highly accurate investigation of line intensity factors within the nu(1)+2nu(2) (0)+nu(3) combination band of carbon dioxide, around 2 microm wavelength, at a temperature of 296.0 K. This relatively complex apparatus enables one to observe the absorption line shape with high precision and accuracy in such a way that it is possible to retrieve the integrated absorbance with a relative uncertainty better than 0.1%. The absorption spectra were interpolated with the uncorrelated strong-collision model of Rautian and Sobel'man in order to take into account Dicke narrowing effects, thus obtaining an agreement at a level of a few parts per 10(-5). We report line strength values for the R(2)-R(18) transitions with an unprecedented level of accuracy, in the range between 0.1% and 0.15%. Finally, we discuss the possibility of providing a first experimental test of the theoretical model for molecular line strengths based on the Herman-Wallis expansion.