A new approach to perform single-electron transfer living radical polymerization (SET-LRP) in water is described. The key step in this process is to allow full disproportionation of CuBr/Me6TREN (TREN = tris(dimethylamino)ethyl amine to Cu(0) powder and CuBr2 in water prior to addition of both monomer and initiator. This provides an extremely powerful tool for the synthesis of functional water-soluble polymers with controlled chain length and narrow molecular weight distributions (polydispersity index approximately 1.10), including poly(N-isopropylacrylamide), N,N-dimethylacrylamide, poly(ethylene glycol) acrylate, 2-hydroxyethyl acrylate (HEA), and an acrylamido glyco monomer. The polymerizations are performed at or below ambient temperature with quantitative conversions attained in minutes. Polymers have high chain end fidelity capable of undergoing chain extensions to full conversion or multiblock copolymerization via iterative monomer addition after full conversion. Activator generated by electron transfer atom transfer radical polymerization of N-isopropylacrylamide in water was also conducted as a comparison with the SET-LRP system. This shows that the addition sequence of l-ascorbic acid is crucial in determining the onset of disproportionation, or otherwise. Finally, this robust technique was applied to polymerizations under biologically relevant conditions (PBS buffer) and a complex ethanol/water mixture (tequila).

Photoinduced living radical polymerization of acrylates, in the absence of conventional photoinitiators or dye sensitizers, has been realized in "daylight'"and is enhanced upon irradiation with UV radiation (λ(max) ≈ 360 nm). In the presence of low concentrations of copper(II) bromide and an aliphatic tertiary amine ligand (Me6-Tren; Tren = tris(2-aminoethyl)amine), near-quantitative monomer conversion (>95%) is obtained within 80 min, yielding poly(acrylates) with dispersities as low as 1.05 and excellent end group fidelity (>99%). The versatility of the technique is demonstrated by polymerization of methyl acrylate to a range of chain lengths (DP(n) = 25-800) and a number of (meth)acrylate monomers, including macromonomer poly(ethylene glycol) methyl ether acrylate (PEGA480), tert-butyl acrylate, and methyl methacrylate, as well as styrene. Moreover, hydroxyl- and vic-diol-functional initiators are compatible with the polymerization conditions, forming α,ω-heterofunctional poly(acrylates) with unparalleled efficiency and control. The control retained during polymerization is confirmed by MALDI-ToF-MS and exemplified by in situ chain extension upon sequential monomer addition, furnishing higher molecular weight polymers with an observed reduction in dispersity (Đ = 1.03). Similarly, efficient one-pot diblock copolymerization by sequential addition of ethylene glycol methyl ether acrylate and PEGA480 to a poly(methyl acrylate) macroinitiator without prior workup or purification is also reported. Minimal polymerization in the absence of light confers temporal control and alludes to potential application at one of the frontiers of materials chemistry whereby precise spatiotemporal "on/off" control and resolution is desirable.

Historical details regarding the genesis of SET-LRP and the evolution from single electron degenerative transfer living radical polymerization (SET-DTLRP) have been addressed in detail in the aforementioned review and will not be revisited herein. The mechanistic debate will also be critically discussed; however, it is not the main focus of this current contribution.

The Jovian Auroral Distributions Experiment (JADE) on Juno provides the critical in situ measurements of electrons and ions needed to understand the plasma energy particles and processes that fill the Jovian magnetosphere and ultimately produce its strong aurora. JADE is an instrument suite that includes three essentially identical electron sensors (JADE-Es), a single ion sensor (JADE-I), and a highly capable Electronics Box (EBox) that resides in the Juno Radiation Vault and provides all necessary control, low and high voltages, and computing support for the four sensors. The three JADE-Es are arrayed 120 • apart around the Juno spacecraft to measure complete electron distributions from ∼0.1 to 100 keV and provide detailed electron pitch-angle distributions at a 1 s cadence, independent of spacecraft spin phase. JADE-I measures ions from ∼5 eV to ∼50 keV over an instanta

This paper describes the science motivation, measurement objectives, performance requirements, detailed design, approach and implementation, and calibration of the four Hot Plasma Composition Analyzers (HPCA) for the Magnetospheric Multiscale mission. The HPCA is based entirely on electrostatic optics combining an electrostatic energy analyzer with a carbon-foil based time-of-flight analyzer. In order to fulfill mission requirements, the HPCA incorporates three unique technologies that give it very wide dynamic range capabilities essential to measuring minor ion species in the presence of extremely high proton fluxes found in the region of magnetopause reconnection. Dynamic range is controlled primarily by a novel radio frequency system analogous to an RF mass spectrometer. The RF, in combination with capabilities for high TOF event processing rates and high current micro-channel plates, ensures the dynamic range and sensitivity needed for accurate measurements of ion fluxes between ∼1 eV and 40 keV that are expected in the region of In order to calibrate the four HPCA instruments we have developed a unique ion calibration system. The system delivers a multi-species beam resolved to M/ M ∼ 100 and current densities between 0.05 and 200 pA/cm 2 with a stability of ±5 %. The entire system is controlled by a dedicated computer synchronized with the HPCA ground support equipment. This approach results not only in accurate calibration but also in a comprehensive set of coordinated instrument and auxiliary data that makes analysis straightforward and ensures archival of all relevant data.

Aqueous single electron transfer living radical polymerization (SET-LRP) has been employed to synthesize multi-block homopolymers and copolymers of a range of acrylamide monomers including N-isopropylacrylamide (NIPAM), 2-hydroxyethyl acrylamide (HEAA), N,N-dimethyl acrylamide (DMA) and N,N-diethylacrylamide (DEA).

A versatile and inexpensive photochemical platform for the preparation of high-order multiblock functional materials.

Dithiomaleimides (DTMs) with alkyl substituents are shown to be a novel class of highly emissive fluorophores. Variable solubility and further functionalization can easily be tailored through the choice of N and S substituents. Inclusion of a DTM unit into a ROP/RAFT initiator or insertion into the disulfide bond of salmon calcitonin (sCT) demonstrates the utility for fluorescent labeling of polymers and proteins. Simultaneous PEGylation and fluorescent labeling of sCT is also demonstrated, using the DTM unit as both a linker and a fluorophore. It is anticipated that DTMs will offer an attractive alternative to commonly used bulky, planar fluorophores.