Efficient Emission Enhancement of Single CdSe/CdS/PMMA Quantum Dots through Controlled Near-Field Coupling to Plasmonic Bullseye Resonators.

A strong increase of spontaneous radiative emission from colloidally synthesized CdSe/CdS/PMMA hybrid particles is achieved when manipulated into plasmonic bullseye resonators with the tip of an atomic force microscope (AFM). This type of antenna provides a broadband resonance, which may be precisely matched to the exciton ground state energy in the inorganic cores. Statistically analyzing the spectral photoluminescence (PL) of a large number of individual coupled and uncoupled CdSe/CdS/PMMA quantum dots, we find an order of magnitude of intensity enhancement due to the Purcell effect. Time-resolved PL shows a commensurate increase of the spontaneous emission rate with radiative lifetimes below 230 ps for the bright exciton transition. The combination of AFM and PL imaging allows for sub-200 nm localization of the particle position inside the plasmonic antenna. This capability unveils a different coupling behavior of dark excitonic states: even stronger PL enhancement occurs at positions with maximum spatial gradient of the nearfield, effectively adding a dipolar component to original quadrupole transitions. The broadband maximization of light-matter interaction provided by our nanoengineered compound systems enables an attractive class of future experiments in ultrafast quantum optics.

Changes in Ocean Heat, Carbon Content, and Ventilation: A Review of the First Decade of GO-SHIP Global Repeat Hydrography.

Global ship-based programs, with highly accurate, full water column physical and biogeochemical observations repeated decadally since the 1970s, provide a crucial resource for documenting ocean change. The ocean, a central component of Earth's climate system, is taking up most of Earth's excess anthropogenic heat, with about 19% of this excess in the abyssal ocean beneath 2,000 m, dominated by Southern Ocean warming. The ocean also has taken up about 27% of anthropogenic carbon, resulting in acidification of the upper ocean. Increased stratification has resulted in a decline in oxygen and increase in nutrients in the Northern Hemisphere thermocline and an expansion of tropical oxygen minimum zones. Southern Hemisphere thermocline oxygen increased in the 2000s owing to stronger wind forcing and ventilation. The most recent decade of global hydrography has mapped dissolved organic carbon, a large, bioactive reservoir, for the first time and quantified its contribution to export production (∼20%) and deep-ocean oxygen utilization. Ship-based measurements also show that vertical diffusivity increases from a minimum in the thermocline to a maximum within the bottom 1,500 m, shifting our physical paradigm of the ocean's overturning circulation.

Probing of chain conformations in conjugated polymer nanoparticles by electron spin resonance spectroscopy.

In the case of conjugated polymer chains usually considered as rigid or stiff, it is an open question how the individual chains adopt their conformation inside nanoparticles. Here, the conformation of such a rigid conjugated polymer chain is elucidated for the first time. For this purpose, electron paramagnetic resonance spectroscopy as a method allowing for a direct observation is established.

Morphological changes during annealing of polyethylene nanocrystals.

Polymer crystals are metastable and exhibit morphological changes when being annealed. To observe morphological changes on molecular scales we started from small nanometer-sized crystals of highly folded long-chain polymers. Micron-sized stripes consisting of monolayers or stacks of several layers of flat-on oriented polyethylene nanocrystals were generated via evaporative dewetting from an aqueous dispersion. We followed the morphological changes in time and at progressively higher annealing temperatures by determining the topography and viscoelastic properties of such assemblies of nanocrystals using atomic force microscopy. Due to smallness and high surface-to-volume ratio of the nanocrystals, already at 75 °C, i.e. about 60 degrees below the nominal melting point, the lateral size of the crystal coarsened. Intriguingly, this occurred without a noticeable reduction in the number of folds per polymer chain. Starting at around 110 °C, chain folds were progressively removed leading to crystal thickening. At higher temperatures, but still below the melting point, prolonged annealing allowed for surface diffusion of molten polymers on the initially bare substrate, leading eventually to the disappearance of crystals. We compared these results to the behavior of the same nanocrystals annealed in an aqueous dispersion and to bulk samples.

Single lamella nanoparticles of polyethylene.

We present a complete analysis of the structure of polyethylene (PE) nanoparticles synthesized and stabilized in water under very mild conditions (15 degrees C, 40 atm) by a nickel-catalyzed polymerization in aqueous solution. Combining cryogenic transmission electron microscopy (cryo-TEM) with X-ray scattering, we demonstrate that this new synthetic route leads to a stable dispersion of individual PE nanoparticles with a narrow size distribution. Most of the semicrystalline particles have a hexagonal shape (lateral size 25 nm, thickness 9 nm) and exhibit the habit of a truncated lozenge. The combination of cryo-TEM and small-angle X-ray scattering demonstrates that the particles consist of a single crystalline lamella sandwiched between two thin amorphous polymer layers ("nanohamburgers"). Hence, these nanocrystals that comprise only ca. 14 chains present the smallest single crystals of PE ever reported. The very small thickness of the crystalline lamella (6.3 nm) is related to the extreme undercooling (more than 100 degrees C) that is due to the low temperature at which the polymerization takes place. This strong undercooling cannot be achieved by any other method so far. Dispersions of polyethylene nanocrystals may have a high potential for a further understanding of polymer crystallization as well as for materials science as, e.g., for the fabrication of extremely thin crystalline layers.

High molecular mass polyethylene aqueous latexes by catalytic polymerization.

Semicrystalline microparticles of high molecular mass polyethylene can be prepared as aqueous dispersions by catalytic emulsion polymerization of ethylene with a mini-emulsified catalyst precursor (D$\rm{\frown}$D=salicylaldimine, L=pyridine). Stable polymer latexes are formed.

Coordination polymerization in water affording amorphous polyethylenes.

The coordination polymerization of ethylene in water as a reaction medium was studied. Rubbery amorphous branched polyethylene was obtained when a known cationic diimine-substituted methyl complex was employed as a catalyst precursor. High rates of up to 900 TOh(-1) (turnover frequency) were observed. In contrast to solution polymerization in an organic solvent, the rate of suspension polymerization in water increases greatly with ethylene pressure in the range up to 20 bar; this indicates control of the polymerization rate by the concentration of the olefin monomer at the catalytically active site. The effect and mode of mass transfer phenomena were studied. A high catalyst stability in the aqueous coordination polymerization was observed. It was found to be due to an "encapsulation" of the water-insoluble catalyst precursor in the hydrophobic amorphous polymer during the polymerization reaction, and this resulted in strongly restricted accessibility for the aqueous phase. Surprisingly, exposure of the water-stable catalyst precursor to ethylene monomer in solution in the presence of water resulted in immediate decomposition. Polymer microstructure, and thermal and mechanical properties were investigated. The different degree of branching, molecular weight, and corresponding macroscopic properties of the polymers obtained in water as a reaction medium versus solution polymerization in methylene chloride under the same conditions are due to the different phase behavior during polymerization (suspension vs. solution), as opposed to an effect of water on the catalytically active centers.